Low density high impact resistant composition and method of forming

ABSTRACT

One or more fly ash materials or other optimized mineral fillers having a particle size distribution that may include cinders of selected sizes is mixed to form a filler. The filler is then mixed with an acid scavenger, an antioxidant, a compatibilizer and an impact modifier into a resin to form either a final composition or a masterbatch. A blowing agent may be added to both. Either the masterbatch or the final composition is mixed with a blend of a mineral oil and a styrenic block copolymer. Thereafter the masterbatch if prepared is mixed into or with a base resin to form the final composition. Fractional melt may be used in the masterbatch and in the final composition. The physical properties of the resulting products can be controlled by varying the ingredients. Some masterbatches are combined to produce products that have improved impact strength and/or that have enhanced toughness when compared to products made using naked or virgin resins. Alternately, the blowing agent may be added just before processing the composition into a final product.

BACKGROUND OF THE INVENTION

1. The Field

A composition is disclosed in which a dry powder or liquid blowing agentis mixed into either a base blend or a liquid mixture. The base blend isformed of one or more dry mineral fillers such as mechanically processedfly ash. Thereafter, the other ingredients are added to the base blendand compounded to form a masterbatch or to form a fully compoundedmaterial both of which are processed at a temperature at which theblowing agent is not activated. More specifically, an acid scavenger, anantioxidant, a suitable carrier resin, a particle compatibilizer and animpact modifier may be mixed with the dry filler blend to form amasterbatch that is thereafter combined with a base resin (which may bethe same as the carrier resin) and an additional low or fractional meltresin to form the fully compounded material. Alternately, all theingredients may be combined at once to form the fully compoundedmaterial. Also, alternately, the composition may be formed as a mixturewithout the blowing agent; and the dry powder blowing agent isthereafter mixed in as that mixture is heated into liquid form justbefore mechanical processing into a product. The final product aftermechanical processing is less dense while having an impact resistanceequal to or greater than the impact resistance of a similar productformed from a base resin having a blowing agent mixed therein.

2. The Relevant Technology

A plastic like polyethylene and/or polypropylene is typically selectedfor desired physical properties, some of which can be controlled usingadditives that include, among others, colorants, lubricants,stabilizers, foaming agents and various fillers. Traditionally, fillershave been used to lower the cost of a composition and in turn theresulting product because expensive resin is being replaced by lessexpensive filler. Specific fillers called reinforcing fillers arc alsoknown to be used to alter some of the physical properties of the baseresin, such as tensile and flexural strength, hardness, impactresistance, shear and other rheological and morphologicalcharacteristics of the resulting compounded material. Blowing agentshave also been used to reduce the amount of resin used but also tocontrol physical properties such as the density of the finished product.

It is known that one may add a blowing agent in the process ofmanufacturing a product while the compounded material is in liquid form.When the blowing agent is activated in the manufacturing process, theblowing agent produces a gas which in turn makes the liquid resin andresulting solid material less dense. In other words, less resin is usedto form essentially the same product thereby reducing the amount ofcompound and in turn base resin used to form a particular product due tothe formation of gas filled bubbles or pockets within the product.

Fillers and blowing agents are also known to have some effect onprocessing characteristics of thermoplastic resins while molten. Forexample, unfilled polymers behave like non-Newtonian fluids withviscosity changing during melt processing. Some additives affect therheology except that increasing the amount of the filler (regardless ofthe shape of the particles of the filler) has been reported to lead toreduced melt elasticity. M. Xanthos, Functional Fillers For Plastics(Wiley-VCH 2005) pp. 32-35.

Fly ash, cinders and combinations of fly ash and cinders have beenidentified as fillers that can be used with resins in a beneficialmanner as disclosed in U.S. Pat. No. 7,879,939 (Prince et al.)(hereinafter the '939 patent).

Fly ash is a waste material that is comprised of various minerals whichare the residue formed during the combustion of hydrocarbons like coal,typically in large volume processes like those associated with thegeneration of electrical power. As the coal is burned, a residue or“ash” is formed that is so light that it can be regarded as buoyant inair. The fly ash may include cinders formed during coal combustion. Thecinders are typically made from fused or other non combustible matterthat was part of the coal. Large cinders typically fall to the bottom inthe combustion zone or area. Some smaller or lighter cinders can becomeentrained in the exhaust stream along with fly ash.

Fly ash, as well as the cinders, can vary in chemical and physicalproperties based on, among other things, the specific source of thehydrocarbon being combusted and the particulars of the combustionprocess. In turn, fly ash, by itself and also together with cinders, hasnot been used as a filler for thermoplastic compositions on a commercialscale because physical and chemical properties are not consistent.

To create a standard or consistent fly ash composition that is suitablefor use on a commercial scale with thermoplastic resins, U.S. PatentApplication Publication No. 2011/0071252 published Mar. 24, 2011 (the'252 Publication) for a “SYSTEM AND METHOD FOR FORMING A COMPOSITIONWITH AN OPTIMIZED FILLER” discloses methods and procedures to select orform an optimized filler or blend of fillers. In other words, fly ash,with and without cinders, can be mechanically treated and blended orotherwise mixed to form a filler or blend of fillers that is useful informing thermoplastic compositions as disclosed in the '939 patent.

It is known to use certain fillers with thermoplastic resins to alterthe toughness or impact resistance properties for the manufacture of awide variety of products. But it has not been known how to formulatesuch products that are both tough and less costly to manufacture and howto formulate to vary the physical properties such as the toughness whilereducing cost and reducing density by use of blowing agents.

BRIEF SUMMARY

A dry mineral filler in powder form such as at least one or more fly ashmaterials having a plurality of ash particles and optionally, a blowingagent in powder form, are mixed together to form a base blend. The baseblend is then mixed with a base resin such as a thermoplastic base resinalong with a fractional or low melt resin, a compatibilizer, and anoil-softened styrenic block co polymer either in such quantities to forma masterbatch for further combination with base resin and/or fractionalor lower melt resin or to form, with sufficient base resin andfractional or low melt resin, the desired composition. Alternately, allthe ingredients except the blowing agent are combined to form a mixtureor final compound that is heated to liquid form for mechanicalprocessing into a product. The blowing agent is injected or mixed intothe mixture in liquid form before the composition is formed into aproduct.

Preferably, the compatibilizer is selected to assist in theinterconnectivity of the particles of the dry mineral filler, such asthe particles of the fly ash, with the thermoplastic base resin. Thecompatibilizer can be a maleated polyolefin or a liquid silane. Acarrier resin may be grafted with maleic anhydride having a melt flowindex selected to encapsulate a plurality of particles of the mineralfiller such as fly ash particles. To form a masterbatch, the materialsare mixed with a base resin and/or fractional melt resin having selectedphysical properties. Alternately the desired composition is formed usingsufficient base resin and/or fractional melt resin.

The mineral filler such as fly ash is selected or mechanically processedso that it has small particles in the submicron (less than 1 micron) tosmaller micron range (less than about 10 microns) to enhance foaming vianucleation of the gas bubbles as they are forming. That is, it has beenlearned that the above stated particle sizes contribute to or facilitatethe excellent dispersion and distribution of the filler particles whencombined with blowing agent and then compounded into a masterbatch or afully formulated pellet. It has also been found that any othercombination of fillers “optimized for flowability” or combination offillers containing particles sufficient to nucleate gas bubble createsan distribution of small cells in structural foam applications.

Also disclosed is a method of forming compositions from a blending of abase resin with a masterbatch that includes a filler formed from fly ashas noted above, along with a carrier resin, an antioxidant, an acidscavenger, and optionally, a compatibilizer and also optionally anoil-softened styrenic block copolymer. Of course a blowing agent isincluded either in dry form or liquid form when blending with the filleror as a powder or a liquid when it is inserted into the meltedcomposition immediately before product formation.

BRIEF DESCRIPTION OF THE DRAWINGS

To further clarify the above and other advantages and features of thepresent disclosed compositions and methods, a more particulardescription will be rendered by reference to the appended drawing. Itshould be understood that the drawing depicts only typical embodimentsand therefore is not to be considered limiting of the scope of theappended claims. More specifically:

FIG. 1 is a diagram of the steps and ingredients used to form acomposition as herein disclosed;

FIG. 2 is a photomicrograph at 5000 magnification of a ComparativeExample;

FIG. 3 is a photomicrograph at 5000 magnification of another ComparativeExample;

FIG. 4 is a photomicrograph at 5000 magnification of an Example;

FIG. 5 is a photomicrograph at 5000 magnification of another Example;

FIG. 6 is a photomicrograph at 5000 magnification of another Example;

FIG. 7 is a photomicrograph at 5000 magnification of another Example;

FIG. 8 is a photomicrograph at 5000 magnification of another Example;

FIG. 9 is an photograph at 10× magnification of a cured polyethylenematerial using a mechanically processed fly ash as a filler;

FIG. 10 is an photograph at 50× magnification of another curedpolyethylene material using a mechanically processed fly ash as afiller;

FIG. 11 is an photograph at 5× magnification of a cured polyethylenematerial with a blowing agent added to the masterbatch and thenprocessed into the masterbatch pellet;

FIG. 12 is an photograph at 10× magnification of a cured polyethylenematerial with a blowing agent added to the final composition (at thethroat of the press) just before the extrusion or injection process;

FIG. 13 is. an photograph at about 10× magnification of a curedpolyethylene material with a blowing agent added but without anymasterbatch that includes a mechanically processed fly ash filler;

FIG. 14 is an photograph at about 10× magnification of a curedpolyethylene material with the same blowing agent and the same amount ofblowing agent as was added to the sample in FIG. 13 along with amechanically processed fly ash in a masterbatch;

FIG. 15 a photograph at 30× magnification of cured polyethylene materialof FIG. 14 with a blowing agent added to the masterbatch which includesfly ash as a filler;

FIG. 16 a photograph at 30× magnification of a cured polyethylenematerial of FIG. 15 with a blowing agent added to the masterbatch; and

FIG. 17 a photograph at 500× magnification of a cured polyethylenematerial of FIG. 16.

DESCRIPTION

The compositions as disclosed include a combination of ingredients oneof which is a foaming agent to produce a material or product that isless dense while retaining improved physical characteristics such ashardness and toughness over resins made only with the foaming agent.

FIG. 1 illustrates a typical process for forming the desiredcompositions exemplified by the data from examples set forthhereinafter. It should also be understood that the drawing and theexamples are not intended to limit the scope of the disclosure or theappended claims. Rather, alternatives, modifications and equivalents arewithin the spirit and scope of this disclosure and the appended claims.

Certain thermoplastic resins are selected to manufacture products thatwill exhibit desired physical properties. Some products need to be softor flexible while others need to be tough and hard. Polyethylene andpolypropylene are typically selected for products that need to have goodimpact resistance (toughness) and good tensile and flexural strength(stiffness). Such materials and their equivalents are typically usedwithout fillers or similar additives.

One example of unmodified thermoplastic resin is generally known as “nobreak” polypropylene copolymer. The compositions of the presentinvention can dramatically increase impact resistance with comparable orbetter tensile strength and flexural strength using a high densitypolyethylene (HDPE) thermoplastic resin which is less expensive than the“no break” polypropylene copolymer while using a foaming agent to reducethe density and in turn the amount of HDPE used to produce a comparableproduct without a foaming agent.

In the manufacture of plastic products, a suitable thermoplastic resinis melted to form a melt into which other ingredients are mixed. Thatcomposition is further melt-processed by molding, extruding,calendaring, and the like, into a final physical plastic shape using anyone of several machines including, for example, vacuum molding machines,extrusion machines and injection molding machines. Speed of manufactureis always an economic consideration so long as the process speed doesnot adversely affect later performance (i.e., physical properties of theproduct). For example, when using injection molding machines to form adesired product with resin to form a composition not modified as hereindiscussed, the cycle time may not be as fast as desired and the coolingtime may be longer than preferred. Cycle time is significant because afaster cycle time means more product is made within a given unit oftime. That increased rate or volume can translate into more productsusing the same number of machines or fewer machines with the sameproduction. In turn, this means that the capital investment may bereduced or controlled so that the cost of manufacture is reduced.

Also, faster cooling time means less space is needed for holding productwhile cooling and in turn less cost associated with establishing andmaintaining necessary manufacturing space.

The process of FIG. 1 leads to the formation of a composition that, whencompared with unmodified thermoplastic resin used commercially, hassignificantly improved impact resistance or toughness propertiesincluding, in some cases, improved comparable tensile strength andflexural strength properties. As will be discussed hereinafter, thephysical properties of the compositions formed and more particularly thepolyethylene compositions formed using the disclosed processes can becontrolled so some desired compositions have significantly increasedimpact characteristics while using materials that lead to lower materialcosts and, in some cases, faster cycle times.

It may also be noted that the compositions being formed as disclosed inconnection with FIG. 1 involve use of any suitable mineral filler inpowder form. While a variety of minerals such as calcium carbonate maybe used. Other mineral material may be used that would otherwise beconsidered waste or residue. For example, fly ash materials are regardedas a waste by-product of combustion. In turn, it can be see that formingcompositions as herein disclosed using fly ash has environmentalbenefits in that the fly ash is being converted from a waste material tomaterial that has a beneficial use consistent with and promotingsustainability principles.

As seen in FIG. 1, a mineral filler 10 is provided which is mechanicallyprocessed 12 by filtering (to remove for example, larger undesiredcomponents and/or demagnetizing as desired to form a mineral powder 14.In preferred applications, the mineral filler is a fly ash material thatis formed from one or more fly ash materials that approach orapproximate an optimized fly ash filler.

When the mineral filler is fly ash, the mechanical process may involvefiltering to remove large cinders and other impurities. Typically theoutput of mechanical processing yields fly ash in which the largestparticle is less than about 900 microns in effective diameter or inwhich the largest particle is about 180 microns in effective diameterconsistent with suitable mechanical processing devices selected by theuser. Of course a large quantity of small sized material that is lessthan 1 micron may also be found passing through the mechanical process12. The mechanical process 12 may also include demagnetizers to removemagnetic particles like iron. Mechanical processing 12 is optional; soit is shown by a dotted line in FIG. 1.

The fly ash from a source is provided as a mineral filler 10 and may besuitable by itself after appropriate mechanical processing 12 andoptional demagnetization 12. A fly ash will be deemed suitable if itmeets a desired mechanical structure (in the form of a fine material orpowder) or particle size distribution that has been empirically found toproduce desired results in the final product. A fly ash may even includecinders of selected sizes in some cases.

If a particular fly ash being supplied does not meet the specificationsdesired, it can be combined with one or more other fly ash materialsthat differ in particle size distribution and possibly in other ways.Each can be suitably mechanically processed and optionally demagnetized12. Thereafter the fly ash from multiple sources can be combined orblended in a fashion as disclosed in U.S. Patent Application PublicationNo. 2011/0071252 published Mar. 24, 2011 (the '252 Publication). Fly ashfrom multiple sources also can be blended empirically or heuristicallyto produce a blend or filler 14 that is suitable for use based on theexperience of the operator. That is, an operator with experience may beable to look at and feel (to determine whether it is fine or coarse andcontains cinders) a plurality of fly ash materials and decide how to mixthem and in what ratio to produce an adequate blend or filler thatapproximates or approaches the optimal blend. An adequate blend can beused in some applications to produce products that are acceptable to theend user.

While the mineral filler 10 is presently entirely fly ash, it should beunderstood that other minerals may be used and that additives can besupplied to be blended into or with the filler. For example, colorantscould be added at this early stage as well as other dry materials thatmay be desirably mechanically mixed or blended with the fly ash. As seenin FIG. 1, a foaming agent 16 may be added in powder or liquid form.

As seen in FIG. 1, the foaming agent 16 is supplied to and mixeddirectly with the filler 14 in a mechanical blending device to form thefiller blend 18.

In some cases a compatibilizer such as a liquid silane 17 coupling agentmay be added 19 to the blend of mineral filler and foaming agent in theblending device 18. The amount of liquid silane used is so small orlimited that it can be added to the dry fly ash and mixed or blended toproduce the filler blend 18, without otherwise affecting the processingproperties of the filler blend 18. That is, the blended filler 18 isstill in powder form. The term “compatibilizer” is a term coined or usedhere to mean that the material is believed to make the association ofthe fly ash particles with the carrier resin more compatible and ineffect facilitates their encapsulation as discussed hereinafter.

As seen in FIG. 1, the blended filler 18 is then mixed with an acidscavenger 30, an antioxidant 32, a thermoplastic carrier resin 34, acompatibilizer 36 (if not otherwise provided) and a fractional or lowmelt index resin serving as the impact modifier 40. The blended filler18, the acid scavenger 30 and the antioxidant 32 are mixed 20 into themelted carrier resin 34 and the compatibilizer 36, which acts toencapsulate the particles of the blended filler 18, in suitablequantities along with a fractional or low melt index resin whichfunctions as an impact modifier 40 to form the masterbatch 38.

Optionally, but preferably, minor amounts of stabilizing additives canbe added to the masterbatch 38. An acid scavenger 30 like hydrotalciteis introduced into the masterbatch 38 in small quantities to reduce theacid that can form when mixing the blended filler 18 and other materialsto form the masterbatch 38. An antioxidant 32 may be a benzene materialsuch as ANOX® NDB® blend available from Chemtura and is introduced tominimize the oxidation when mixing the 38. Chemtura has officesthroughout the world with offices in Middlebury, Conn. ALKANOX® is aphosphorous based antioxidant that can be used and is available alsofrom Chemtura and may be used as an antioxidant. Combinations of ANOX®and ALKANOX® antioxidants may be used as well.

The impact modifier 40 is a fractional melt resin that has a melt flowindex (MFI) at or below 2 and typically a melt flow index of less than1, as measured using ASTM D1238. The impact modifier 40 may even berecycled plastic or waste production called “regrind”, adding to thesustainability features of the invention. Typically, the impact modifier40 selected is lower in cost than the base resin 42 while maintainingcomparable physical properties for the product 46 to those if the baseresin 42 was used without the impact modifier 40. Marlex® HHM 5202 highdensity polyethylene and Marlex® HHM 5502 high density polyethylene(HDPE) available from Chevron Phillips Chemical Company of Woodlands,Tex. have been found to be particularly suitable as an impact modifier.

Styrenic block copolymer, such as SEPTON® copolymer may also function asan impact modifier 40. SEPTON® copolymer comes in pellet form and can beadded directly into the masterbatch 38 as it is being mixed 26 SEPTON®copolymer also comes in flake form (such as SEPTON® 4033) which shouldbe combined or blended 23 with a mineral oil 24 in order for the SEPTON®copolymer 22 to melt sufficiently at normal extrusion temperatures usedto melt-process the masterbatch 38 and/or base resin. The amount of oilused to combine with the SEPTON® 4033 affects the elasticity of themasterbatch 38 and even the final composition 44. Different amounts andkinds of mineral oil can be used to control the elasticity. The use of ablend 23 of SEPTON® 4033 and mineral oil typically in a 90/10 ratio ispreferred.

Inasmuch as the filler blend 18 is a mineral composite and may be aceramic or ceramic-like material in particulate form (e.g., a powder)among molten thermoplastics, it is believed to be important that eachparticle of the filler blend 18 be at least partially coated, andideally totally encapsulated. At present, total encapsulation of theparticles is believed to be accomplished by a compatibilizer, such asthe liquid silane 17 identified, or preferably by a functionalizedpolyolefin compatible with the base resin and reactive with or capableof physical association with the surface of each fly ash particle. Apolyolefin grafted with maleic anhydride, also called a maleatedpolyolefin, with a melt flow index sufficiently low to facilitate somecoating of the fly ash particles is preferred because it is believedthat the wetting of the fly ash particles is enhanced when it is heatedand mixed with the filler particles. Polybond®3009 compatibilizer, whichis also sold by Chemtura, is a maleated HDPE that has been found to beparticularly suitable as the carrier resin 34 for the masterbatch 38 toform the desired compositions.

Without being limited to a particular theory, it is believed that thefly ash particles couple with, and effect a covalent bond with, thePolybond® 3009 material. At the same time, the Polybond® 3009 isbelieved to function as a compatibilizer between the particles and thebase resin 42 to enhance the mixing with, and dispersion of theparticles into, the base resin 42. It is also believed that thePolybond® 3009 acts as a compatibilizer for the various base resins 42being used in the final composition 44, helping them to have a moreeffective blending of different resin types. As an alternate to themaleic-anhydride-modified high density polyethylene, a maleic anhydridegrafted oil, maleic anhydride grafted liquid monomer or a maleicanhydride grafted liquid polymer maybe used to coat as much of thesurfaces of the particles of the filler 24 as possible. A small portion(2% to 5%) of the liquids (like an oil or a liquid polymer) can be usedto coat the particles by blending them in a suitable blender like aHenschel high intensity blender or a continuous flow ribbon blender inthe process of forming the masterbatch 38.

As seen in FIG. 1, the masterbatch 38 is supplied for further mixing 26with a base resin 42. The base resin 42 can be considered a “target”resin because it is recognized that the masterbatch 38 is beingformulated or formed to be mixed with it by a manufacturer in the finalmelt shaping of a product 46 by any recognized production device 48(e.g., injection molding, flow molding, extruding, vacuum molding). Thatis, the base resin 42 is combined with the masterbatch 38 to form thecomposition 44 that is used in the manufacture 48 of a product 46. Thebase resin 42 may be any suitable polyethylene. ExxonMobil 6605.70 HDPE(0.948 Density; 5 g/10 min MFI); Dow DMDA-8007 NT 7 HDPE (0.965 Density;8.3 g/10 min. MFI); and Marlex 9708 HDPE (0.962 Density; 8 g/10 min.MFI)have been found suitable as a base resin 42 in the samples tested todate as discussed hereinafter.

A suitable mineral oil 24 is mixed with a high performance stryrenicblock copolymer 22. The resulting blend 23 softens and enhances theflowability of the composition 44 when in melt form as it is mixed 56while contributing to the strength and elasticity of the final product46. That is, the base resin 42 and the masterbatch 38 create acomposition in melt form that could wet the surfaces of the processingequipment and reduce the production cycle time or throughput time.Adding the blend 23 of the mineral oil 24 and the copolymer 22contributes to the flowability of the composition 44 and is alsobelieved to contribute to the toughness of the product 46. In practice,it has been found that SEPTON® 4033 flakes available from KurarayAmerica, Inc. of Houston, Tex. are particularly useful as the copolymer22. Hydrobite® 550 PO white mineral oil offered by Sonneborn, LLC ofMahwah, N.J. has been found to be particularly useful as the mineral oil24. In use, it has been found that the blend 23 is best when mixed in aratio of about nine units of copolymer to one unit of oil 24. Othersimilar mineral oils such as Penreco® Drakeol® mineral oil arc alsobelieved to be suitable for use.

The masterbatch 38 is typically converted to pellets or a similar solidmechanical shape as an intermediate product and transported to alocation selected for preparing the composition 44, which can be thefinal product or also another intermediate product, depending on thetype of processing equipment used to make the composition 44. Thequantities of filler blend 18, acid scavenger 30, antioxidant 32,carrier resin 34 and compatibilizer 36 are selected such that when themasterbatch 38 is mixed with pre-selected amounts of the base resin 42,the desired amount of blended filler 18 is introduced into, dispersedwithin, and constantly maintained within the composition 44.

The masterbatch 38 is typically in a dry solid form such as pellets, andthe base resin 42 is also typically in a dry solid form such as pellets.The masterbatch 38 and the base resin 42 can be mixed to form a dryblend 54 using a dry pellet blender like one made by Maguire ProductsInc. of Aston, Pa. The dry blend of materials is effectively thecomposition 44 that is introduced into a suitable manufacturing machine48, like an injection molding machine.

In some applications, the base resin 42 along with the masterbatch 38are melted and blended or mixed 26 with the blend 23 to foam thecomposition 44 of any conceivable finally shaped form. As identifiedpreviously, “no break” polypropylene copolymer (COPP) is an unmodifiedthermoplastic resin. HDPE compositions of the invention, as shown in theexamples below, are effective and advantageous replacements for suchCOPP resins presently being evaluated for use in the manufacture ofwheeled carts which are also recognized by homeowners and others aswheeled trash cans in multiple sizes ranging from about 30 gallons insize up to about 100 gallons in size. Such wheeled trash cans must beextremely durable, tough, stiff, and strong in repeated usage in variousclimates and weather conditions over a number of years.

It may be noted that the use of fractional or low melt resin 60 as animpact modifier 40 beneficially affects the overall cost of thecomposition 44. The fractional melt 60 is believed to be available at aprice that is less than the price of the base resin 42. While fractionalmelt materials are being used as the impact modifier 40, it should beunderstood that other low melt index (melt flow index (MFI) less thanabout 2 or 3) materials should be also suitable for use as the impactmodifier 40. Further, one can use reprocessed or reground sources as theimpact modifier 40, further lowering the cost of the resultingcomposition 44. Reprocessed or “regrind” may be used for the base resinas well as fractional and low melt resins used in forming thecompositions 44 as evident from the various samples or examples thatfollow in Tables 2-21 hereinafter.

Of course, it may be noted that the masterbatch 38 contains a notableportion and sometimes a weight majority of fly ash as blended filler 18.Fly ash and fly ash with cinders are products of combustion andotherwise considered a waste or residue as hereinbefore stated. Use of ablended filler 18 in the composition 44 further lowers its cost becausethe blended filler 18 replaces or reduces the amount of base resin 42used in forming a particular product. In other words, a waste material,namely, fly ash (and sometimes fly ash with cinders), is being convertedfrom a waste that must be disposed of (e.g., like transported to a landfill) to a beneficial use that not only eliminates the waste but alsoreduces the amount of expensive resin used in forming a particularproduct while enhancing desired physical properties. Further, it hasbeen noted that the use of fly ash as a blended filler 18 increases theflowability of the masterbatch 38 and the composition 44 so that lessenergy is needed to pump the composition in the manufacturing processleading to significant savings in energy over time. Similarly somecompositions are made with a heat or melt index that is lower than neatresin so that less energy is needed to heat and melt the resin and inturn leading to less time to cool. In turn the manufacturing process canbe faster. That is, the cycle time to form one product is reduced.

Notwithstanding the use of fractional or lower melt index materials asthe impact modifier and the use of a substantial amount of filler blend18, it has been noted that the mechanical characteristics of theresulting product(s) 46 are comparable to the unmodified thermoplasticresins currently commercially used, and in many cases better than thoseresins. In other words, use of the filler 24 with the impact modifier 40leads to savings in energy and savings in material because one is usingless resin while using or consuming a waste material like fly ash. Atthe same time, the resulting product has physical properties that arethe same as or better than the naked or pure resin.

Alternately, the foaming agent 16 or blowing agent may not be added tothe blend filler 18. Rather the foaming agent 16 is supplied for directincorporation with the composition 44. In turn the material formed intoa masterbatch 38 has all the same ingredients except for the foamingagent 16. While FIG. 1 shows the foaming agent 16 being supplied forincorporation with the mixture 47 from the mixing 26 via line 15, itshould be understood that the foaming agent 16 maybe mixed into thecomposition 15 in liquid form or into the material supply portion of amachine that is heating the composition 44 in the manufacturing process48.

Testing was undertaken by following steps in a sequence that is believedto be required to achieve the desired results. First the mineral filler10 was selected to be fly ash which is processed by suitable mechanicalmeans 12 like sifting and demagnetization. A foaming agent 16 is alsoselected to be in powder form and then blended using procedures tooptimize the particular particle size distribution that is less thanabout 900 microns in effective diameter. The foaming agent 16 and themineral filter 10 (fly ash) are combined to form the filler blend 18.Liquid silane 17 in small quantities may be supplied 19A as a separateingredient to the mix 26 as hereinafter discussed. The amount of silane17 added is so small that it does not impact on the physical form of thefiller blend 18. That is, the filler blend remains a powder. The liquidsilane 17 may also be added optionally as shown by dotted line 19B.

The carrier resin 34 can also be regarded as or function as acompatibilizer 36. However a separate compatibilizer 36 is preferred.The carrier resin 34, the compatibilizer 36, and the impact modifier 40are melted and mixed together 20 along with an acid scavenger 30, one ormore antioxidants 32 and the blend filler 18 in forming the masterbatch38. Notably an impact modifier 40 can also be mixed with the finalcomposition as desired.

Based on test results to date, it is believed that the blended filler 18may be from about 0.2% percent to about 95 percent by weight of themasterbatch 38. The acid scavenger 30 may be from about 0.1 percent toabout 10 percent by weight of the masterbatch and the antioxidant 32 maybe from about 0.2 percent to about 1.0 percent by weight of themasterbatch 38. The carrier resin 34 that also functions as acompatibilizer may be from about 15 to about 70 percent by weight of themasterbatch 38. The impact modifier 40 may be from about 10 to about 40%by weight of the masterbatch 38. In normal practice, the materials aremelt-mixed 20 and then extruded as pellets for further processing whenre-melted and mixed 26 with other materials to form the composition 44as hereinafter discussed.

In some applications, the copolymer/oil blend 23 is added either formixing 26 to form the composition 44 or via line 21 for mixing 20 toform the masterbatch 38. The blend 23 is formed by first mixing amineral oil 24 with the copolymer to form a blend 23 that is in a flakeform. The blend 23 is about 60-95% of the copolymer 22 and from about 5to about 300% mineral oil 24 (or a ratio as high as 3 parts oil to 1part copolymer or as low as 20 parts copolymer to 1 part oil) 22 whichis heated or melted to form the blend 23 that is optionally added to themix 20 or to the mix 26. But in all cases, the copolymer 22 and oil mustfirst be mixed to form the blend 23, an oil-softened styrenic blockcopolymer.

The masterbatch 38 as an intermediate product which is a concentrate.The ratio of materials is selected to be in suitable proportion to beadded to or mixed with the base resin 42 to form the composition 44. Thecomposition 44 can have from about 1 percent to about 70 percent byweight of the masterbatch with the remainder being base resin 42. Insome applications, a separate supply of low melt index or fractionalmelt material 60 can be added in lieu of base resin 42. In someapplications, the amount of fractional melt 60 or low melt indexmaterial may be from about 1 to about 35 percent by weight of thecomposition while the base resin 42 can be from about 20 to about 98percent by weight of the composition 44.

Table 1 following shows the composition of six different materials(Masterbatches I-VI) which function as the masterbatch 38 without ablowing agent like blowing agent 16. That is, the blowing agent 16 issupplied via line 15 directly to the composition 44 as it is beingheated for mechanical processing (e.g., injection molding).

The Masterbatches I-VI were used to prepare samples of a composition 44that are numbered 1-64. As seen in Table 1, Masterbatches I-VI allinclude a mineral filler 10 which is a fly ash blend called Blend Bsupplied by Revolutionary Plastics, LLC of Las Vegas, Nev. Masterbatch Iis a composition that is available from Poly One Corporation of AvonLake, Ohio and was used in the formation of base line materials used forcomparison discussed here after. Comparative Examples A, F, J, L and Tare controls of a base resin 42. Comparative Examples R and S arecontrols of fractional melt resins.

Masterbatches II-VI in Table 1 can also be seen to include an acidscavenger which functions as the acid scavenger 30 discussedhereinbefore. It also shows use of an antioxidant that functions as theantioxidant 32 discussed hereinbefore. Masterbatches III-VI all use ablend to function as the blend 54 that is supplied in this case as shownby dotted line 55 for mixing 28 to form the masterbatch 38. The blend 54is formed of 4.5% Septon and 0.5% mineral oil. Stated alternately, theblend 54 is 90% Septon and 10% mineral oil. Masterbatches IV-VI can alsobe seen to include different kinds of fractional melt materials asshown. The Masterbatches II-VI as well as Comparative Examples B and Cand Examples or samples 1-71 were all prepared by mixing the variousingredients at about 232° C. in an injection molding machine; exceptthat the blend 54 was pre-mixed before being added.

It may be noted that MasterBatches I-VI do not include the foaming agent16. That is, the foaming agent is not introduced via line 15 to thecomposition 47 before or as it is being mechanically processed. It hasbeen the industry practice to develop and test resins and compositionsbefore foaming and to compare the test results of such resins andcompositions before foaming using a blowing agent. Applicant believesthat the industry practice is to assume that any change in physicalcharacteristic of a resin or composition experienced before foamingusing a blowing agent will be lead to similar changes in the foamedmaterial after foaming. Thus one may compare a resin with a compositionand note a change in, for example, the Notched Izod impact test (ASTMTest D256), from about 3 to about 12. After foaming or addition andactivation of the blowing agent of the same resin and composition, arelative or comparable change or increase in the Notched Izod testresults is expected and obtained even though no measurements or testsare normally or typically performed on the foamed material to confirmwhat is empirically observed.

TABLE 1 MASTERBATCH MATERIALS Ingredient I II III IV V VI Eclipse FlyAsh Blend B (Revolutionary Plastics, Las 75 70 70 70 70 70 Vegas, NV)Chevron TR935 MDPE 23.8 Hydrotalcite acid scavenger 0.5 0.5 0.5 0.350.35 0.35 Chemtura Anox NDB antioxidant 0.35 0.35 0.35 0.245 0.245 0.245Chemtura Alkanox antioxidant 0.35 0.35 0.35 0.245 0.245 0.245 ChemturaPolyBond 3009 maleated polyethylene 28.8 14.4 5 5 5 (0.95 Density; 3-6g/10 min. MFI) Kuraray Septon 4033 SBC Flakes 12.96 4.5 4.5 4.5Sonneborn 550 Mineral Oil 1.44 0.5 0.5 0.5 Marlex HHM 5202BN HDPE (0.951Density; 0.35 g/ 19.16 10 min. MFI) Marlex HHM 5502BN HDPE (0.955Density; 0.35 g/ 19.16 10 min. MFI) Westlake EN1807AA HDPE (0.921Density; 0.7 g/10 min. 19.16 MFI) Total 100 100 100 100 100 100

In order to demonstrate the improvements including the ability to varyphysical parameters as discussed herein before, a number of base resinsand a number of samples were prepared to demonstrate the physicalparameters of the various compositions and base resins all withoutblowing agent added. The following Tables 2-10 show the physicalcomposition of the base resins tested and the physical composition of 71samples. Tables 11-21 show the results of tests which show physicalparameters or characteristics of the base resins and samples. In Tables2-21, the capital letters (e.g., “A”) are for base resins and numbers(e.g., “1, 2, 3”) are for test samples. In some cases, the numbers arefollowed by a letter like sample 1 A and 52 B purely for administrativeconvenience. The compositions are each different upon comparison of theingredients.

The same letters and numbers are used for the same materials throughoutTables 2-21. Thus, for example, capital “C” in Table 2 refers to a baseresin that is formed by mixing 50% of a particular Exxon Mobil baseresin as shown with 30 percent of Marlex material as indicated used asan impact modifier and 20% of the Masterbatch I from Table 1. As anotherexample, the number “2” refers to a composition that includes 50% of anExxonMobil base resin as shown along with 28.5% of Marlex as shown and21.5% of Masterbatch TIT. From time to time, different base resins weretested and/or retested to confirm and/or reconfirm results. Thus, baseresin A and base resin F are in fact what is sometimes referred to asvirgin or neat resin and are the same material, but tested at differenttimes. Base resin B and C are compositions that use Masterbatch I toshow other base resin compositions that cannot attain the benefits thatevolve in the other key tested samples.

In reference to Tables 2-21, some tables are vertically longer and areshown with a part A and B. The individual columns for each such Tablecontinue from part A to part B.

TABLE 2 Example (Wt. %) A B C 1 1A 1B 2 F ExxonMobil 6605.70 100 80 5045 78.5 50 50 100 HDPE (0.948 Density; 5 g/ 10 min MFI) Marlex HHM5202BN 30 28.5 28.5 28.5 HDPE (0.951 Density; 0.35 g/10 min. MFI)Kuraray Septon 4033 SBC 4.5 Flakes Sonneborn 550 Mineral 0.5 OilMasterbatch I 20 20 Masterbatch II 21.5 21.5 21.5 Masterbatch III 21.5Total 100 100 100 100 100 100 100 100

TABLE 3 Example (Wt. %) 3 4 5 G 6 H 7 8 9 A ExxonMobil 6605.70 HDPE(0.948 50 45 73.5 50 100 50 50 50 Density; 5 g/10 min MFI) Marlex HHM5202BN HDPE (0.951 28.5 32.6194 28.5 28.5 Density; 0.35 g/10 min. MFI)Marlex HHM 5502BN HDPE (0.955 28.5 28.5 Density; 0.35 g/10 min. MFI)Kuraray Septon 4033 SBC Flakes 4.5 4.5 0.9675 Sonneborn 550 0.5 0.50.1075 Mineral Oil Chevron ALN 070 “No Break” 100 PolypropyleneCopolymer (0.9 Density; 7 MFI) Hydrotalcite acid scavenger 0.07525Chemtura Anox NDB antioxidant 0.05268 B Chemtura Alkanox antioxidant0.05268 Chemtura PolyBond 3009 maleated 1.075 polyethylene (0.95Density; 3-6 g/10 min. MFI) Eclipse Fly Ash Blend B 15.05 (RevolutionaryPlastics, Las Vegas, NV) Masterbatch III 21.5 21.5 Masterbatch IV 21.521.5 Masterbatch V 21.5 21.5 Total 100 100 100 100 100 100 100 100 100

TABLE 4 Example (Wt. %) 10 11 12 13 14 15 16 17 18 19 ExxonMobil 6605.7050 50 50 50 50 50 50 50 50 50 HDPE (0.948 Density; 5 g/ 10 min MFI)Marlex HHM 5202BN 28.5 28.5 14.25 14.25 HDPE (0.951 Density; 0.35 g/10min. MFI) Marlex HHM 5502BN 28.5 14.25 14.25 HDPE (0.955 Density; 0.35g/10 min. MFI) Westlake EN1807AA 28.5 28.5 28.5 14.25 14.25 14.25 14.25HDPE (0.921 Density; 0.7 g/10 min. MFI) Masterbatch IV 21.5 21.5 21.521.5 Masterbatch V 21.5 21.5 Masterbatch VI 21.5 21.5 21.5 21.5 Total100 100 100 100 100 100 100 100 100 100

TABLE 5 Example (Wt. %) 20 21 I 22 23 24 25 26 27 J A ExxonMobil 6605.7050 50 HDPE (0.948 Density; 5 g/ 10 min MFI) Dow DMDA-8007 NT 7 100 50 5050 50 50 50 HDPE (0.965 Density; 8.3 g/10 min. MFI) Marlex 9708 HDPE 100(0.962 Density; 8 g/10 min. MFI) Marlex HHM 5202BN 14.25 28.5 32.619428.5 HDPE (0.951 Density; 0.35 g/10 min. MFI) Martex HHM 5502BN 14.2528.5 HDPE (0.955 Density; 0.35 g/10 min. MFI) Westlake EN1807AA 14.2514.25 28.5 28.5 HDPE (0.921 Density; 0.7 g/10 min. MFI) B Kuraray Septon4033 0.9675 SBC Flakes Sonneborn 550 Mineral 0.1075 Oil Hydrotalciteacid 0.07525 scavenger Chemtura Anox NDB 0.05268 antioxidant ChemturaAlkanox 0.05268 antioxidant Chemtura PolyBond 1.075 3009 maleatedpolyethylene (0.95 Density; 3-6 g/10 min. MFI) Eclipse Fly Ash Blend B15.05 (Revolutionary Plastics, Las Vegas, NV) Masterbatch IV 21.5 21.5Masterbatch V 21.5 21.5 Masterbatch VI 21.5 21.5 21.5 Total 100 100 100100 100 100 100 100 100 100

TABLE 6 Example (Wt. %) 28 29 K 30 31 32 33 34 35 36 A Marlex 9708 HDPE50 50 50 50 50 50 50 50 50 50 (0.962 Density; 8 g/10 min. MFI) MarlexHHM 5202BN 28.5 32.6194 28.5 28.5 14.25 HDPE (0.951 Density; 0.35 g/10min. MFI) Marlex HHM 5502BN 28.5 14.25 HDPE (0.955 Density; 0.35 g/10min. MFI) Westlake EN1807AA 28.5 28.5 28.5 14.25 14.25 HDPE (0.921Density; 0.7 g/10 min. MFI) Kuraray Septon 4033 0.9675 SBC FlakesSonneborn 550 Mineral 0.1075 Oil Hydrotalcite acid 0.07525 scavengerChemtura A nox NDB 0.05268 antioxidant B Chemtura Alkanox 0.05268antioxidant Chemtura PolyBond 3009 1.075 malcated polyethylene (0.95Density; 3-6 g/10 min. MFI) Eclipse Fly Ash Blend B 15.05 (RevolutionaryPlastics, Las Vegas, NV) Masterbatch IV 21.5 21.5 Masterbatch V 21.521.5 21.5 21.5 21.5 Masterbatch VI 21.5 21.5 Total 100 100 100 100 100100 100 100 100 100

TABLE 7 Example (Wt. %) 37 38 39 40 41 42 L 43 44 45 ExxonMobil 6605.70100 60.8 55.4 50 HDPE (0.948 Density; 5 g/ 10 min MFI) Marlex 9708 HDPE(0.962 50 50 50 50 50 50 Density; 8 g/10 min. MFI) Marlex HHM 5202BN28.5 14.25 14.25 HDPE (0.951 Density; 0.35 g/10 min. MFI) Marlex HHM5502BN 14.25 28.5 14.25 28.5 28.5 28.5 HDPE (0.955 Density; 0.35 g/10min. MFI) Westlake EN1807AA 14.25 14.25 14.25 14.25 HDPE (0.921 Density;0.7 g/10 min. MFI) Masterbatch IV 21.5 21.5 21.5 Masterbatch V 10.7 16.121.5 Masterbatch VI 21.5 21.5 21.5 Total 100 100 100 100 100 100 100 100100 100

TABLE 8 Example 46 47 48 49 50 51 52 52A 52B 52C ExxonMobil 6605.70 44.739.35 60.8 55.4 50 44.7 39.35 89.3 83.9 78.5 HDPE (0.948 Density; 5 g/10 min MFI) Marlex HHM 5502BN 28.5 28.5 14.25 14.25 14.25 14.25 14.25HDPE (0.955 Density; 0.35 g/10 min. MFI) Westlake EN1807AA 14.25 14.2514.25 14.25 14.25 HDPE (0.921 Density; 0.7 g/10 min. MFI) Masterbatch V26.8 32.15 10.7 16.1 21.5 26.8 32.15 10.7 16.1 21.5 Total 100 100 100100 100 100 100 100 100 100

TABLE 9 Example (Wt. %) 52D 52E R S T 53 54 55 56 57 ExxonMobil 6605.7073.2 67.85 100 36.75 32.75 28.75 24.5 20.5 HDPE (0.948 Density; 5 g/ 10min MFI) Marlex HHM 5202BN 100 HDPE (0.951 Density; 0.35 g/10 min. MFI)Marlex HHM 5502BN 100 28.25 27.25 26.25 25.5 24.5 HDPE (0.955 Density;0.35 g/10 min. MFI) Masterbatch V 26.8 32.15 35 40 45 50 55 Total 100100 100 100 100 100 100 100 100 100

TABLE 10 Example (Wt. %) 58 59 60 61 62 63 64 ExxonMobil 6605.70 16.536.75 32.75 28.75 24.5 20.5 16.5 HDPE (0.948 Density; 5 g/ 10 min MFI)Marlex HHM 5502BN 23.5 14.125 13.625 13.125 12.75 12.25 11.75 HDPE(0.955 Density; 0.35 g/10 min. MFI) Westlake EN1807AA 14.125 13.62513.125 12.75 12.25 11.75 HDPE (0.921 Density; 0.7 g/10 min. MFI)Masterbatch V 60 35 40 45 50 55 60 Total 100 100 100 100 100 100 100

As noted before, the compositions disclosed are composed of ingredientswhich can be varied to vary certain physical characteristics of theresulting product like product 46. Impact resistance is an importantcriteria for many compositions 44 and the resulting products 46. SamplesA, B, C, and F were prepared by heating the ingredient or ingredients asnoted in the Table 2 in a suitable blender operating at 232 degreesCentigrade (° C.). The blending or mixing effected by and in aninjection molding machine has been found to be suitable. As notedhereinbefore, a blowing agent may also be inserted when the material 47is liquid but below the temperature to activate. Activation occursshortly thereafter as the liquid material 47 with blowing agent 16 (tobecome the equivalent of composition 44) is heated up in or forprocessing in a mechanical machine (e.g., an extruder) in themanufacturing process 48.

Table 11 presents test data for Samples A, B, C and F. The “neat” or“virgin” resin that is sample A has an impact resistance of 3.896.Sample G in Table 3 is a “no break” polypropylene copolymer which hasimpact resistance seen in Table 12 of 2.785. In turn we can see thatgiven that increased hardness is desired for many products, the impactresistance needs to be greater than about 2.8 to exceed the performanceof “no break” resin and greater than 3.9 in order to exceed theperformance of “naked” or “virgin” HDPE resin.

Comparative Examples B and C had impact resistances well below 2.0 usingMasterbatch I, with or without the addition of fractional melt resin,the impact resistance is about which 1.223 and 1.229 respectively whichis less than the impact resistance of the neat resin that is sample A.The reduction in impact resistance is believed to be attributable to theabsence of a suitable amount of what has been identified as acompatibilizer like compatibilizer 36. Comparative Examples 1A and 1Balso were noted to have an impact resistance less than “neat” resin Aand when using Masterbatch II, which contained a large amount ofPolybond® compatibilizer but no oil-softened Septon® styrenic blockcopolymer. At the same time, it can be seen that sample 1B had an impactresistance of 2.735 which is comparable to the impact resistance of2.785 of the “no break” copolymer that is sample G. Thus sample 1B canbe seen to be a desired composition because it uses a fractional meltwhich can be “regrind” (recycled or reground material reconfigured to beuseful as a resin), plus Masterbatch II that contains fly ash. In turn,the amount of base resin like Exxon Mobil 6605, used for a compositionlike composition 44 is reduced leading to potential savings because lessbase resin (replaced by fly ash filler 24) is used while the impactresistance is essentially the same and the flexural modulus is enhancedsubstantially more than 50%.

Turning now to sample or Example 1, we see from Table 2 that it includes45% of a “neat” or base resin plus 28.5 percent of a fractional melt.Example 1 also has 5% of a blend of mineral oil and Septon® materialplus 21.5% for Masterbatch II. From Table 11 we see that sample orexample 1 has in impact resistance of 10.08 which is over 2.5 timesbetter than “neat” resin like sample A. At the same time, the flexuralmodulus increased from 45,246 to 61,623. In turn, the product 46resulting from the sample 1 is tougher and more flexible. Compared to a“naked” resin line sample A, sample 1 used only half a base resin 42while using a notable amount of fractional melt 60 and Masterbatch IIthat contains fly ash blend as filler 24. Thus sample or Example 1demonstrates that a composition can be prepared that leads to productwith enhanced physical properties like enhanced impact resistance andflexural modulus while reducing the amount of “neat” resin and allowingone to use fractional melt or low melt index materials and a fly ashblend filler 24 to reduce the cost of the composition 44 and theresulting product 46.

Samples or Examples 2, 4, and 5 used Masterbatch III which varied thetypes of compatibilizer added to composition 44 while adding the mixturethe blend 54 of oil-softened Septon SBC into the Masterbatch III and IVvia line 55 along with different types and amounts of fractional melt.Example 2 showed an notable increase in impact resistance with Examples4 and 5 showing significant increase in the impact resistance. AlthoughExample 5 showed that fractional melt resin could be excluded from themix 56, it was added to the masterbatch mixtures. The preference is forthat fractional melt resin to be present in the composition 44 becausethe tensile strength in reduced by approximately one third while theimpact resistance is more than tripled.

As mentioned above, Examples 6 and 7 explored the use of Masterbatch IV.Although Example 6 was roughly comparable in performance to “no break”polypropylene copolymer resin (Comparative Example G) and thereforeacceptable overall, it was generally inferior to neat ExxonMobil HDPEresin (Comparative Example H). Example 7 showed increased impactstrength over Comparative Example H, which indicates a preference foruse of Masterbatch IV to fully mix the Polybond compatibilizer, theblend 54 of oil-softened Septon SBC, and the trio of stabilizeringredients into fractional melt resin as the carrier. Masterbatch IVused less of expensive Polybond compatibilizer and oil-softened SeptonSBC in favor of inexpensive fractional melt resin.

Unexpectedly, reduced amounts of Polybond compatibilizer and the blend54 of oil-softened SBC did not detract from the overall physicalperformance of the composition 44. Examples 7-21 demonstrate aprogression of increasing impact resistance properties based upon use ofMasterbatches IV, V, and VI. Masterbatches IV-VI differ only in the typeof fractional melt resin used. Examples 7-21 demonstrate obtaindifferent and preferably desired impact resistance ranging from 4 to 11while maintaining comparable tensile strength and flexural strength toneat resin of HDPE or “no break” polypropylene copolymer.

For those industries which rely upon “no break” polypropylene copolymer,the significance of the ability to use a polyethylene compound cannot beoverstated. Polyethylene allows one to have faster processing speeds; sothere is a production cost savings. In view of the compositions hereinset forth, one is able to control certain physical characteristics ofthe end product 46 and indeed in many cases obtain enhanced or improvedphysical characteristics like impact resistance.

Comparative Example “I” (“eye”) seen in Table 5 shows use of DowDMDA-8007 High Density Polyethylene (“HDPE”) as an alternate base resin.Examples 22-27 show data for different combinations includingcombinations that use Masterbatches IV, V, and VI. The performancecharacteristics are seen in Tables 14 and 15. Some differences inperformance between Examples 22-27 as well as preceding Examples 7-21are believed to be attributable to different melt flow indexes. Eventhough some of the physical characteristics of the resulting product 46were reduced, they demonstrate the ability to control the physicalcharacteristics and demonstrate acceptable physical characteristics.

With the exception of Comparative Example K, previously discussed, theExamples 28-64 are compositions that are compared with severalComparative Examples J, L, R, S and T in Tables 6-10. These samplesdemonstrate the ability to control the HDPE base resin 42, whileproducing acceptable formulations as evident from the data in Tables15-21.

TABLE 11 Example A B C 1 1B 1C 2 F A Specific Gravity 0.943 1.041 1.0181.04 1.043 1.047 1.046 0.941 ASTM D792 Shore D Hardness 61 62 62 59 6162 61 60 (ASTM D2240) Moisture Test using 0.053 0.066 the SartoriusMoisture Analyzer (%) Ash Test (ASTM D 15.442 11.250 14.680 15.07615.140 15.122 5630-06) (%) ASTM D256 3.896 1.223 1.239 10.08 1.503 2.7356.354 3.974 Impact Resistance (ft-lbf/in) ASTM D256 9.739 3.058 3.09725.2 3.758 6.838 15.885 9.936 Impact Strength (ft-lbf/in2) ASTM D6382,811 2,561 2,538 2,749 3,019 3,136 2,981 2,853 Type 4 Rigid TensileStrength Stress Yield (psi) 3 in/min. B ASTM D638 109,608 128,758123,987 121,923 150,423 164,499 150,180 113,906 Type 4 Rigid TensileModulus Youngs Modulus (psi) 3 in/min ASTM D790 1,078 1,230 1,485 1,2081,303 1,452 1,231 1,021 Flexural Strength Bending Strength @ Peak(lbf/in2) ASTM D790 45,246 61,559 55,467 61,623 71,738 75,730 56,463Flexural Modulus Bending Modulus (lbf/in2)

TABLE 12 Example 3 4 5 G 6 H 7 8 A Specific Gravity 1.046 1.041 1.0410.9 1.042 0.941 1.038 1.057 ASTM D792 Shore D Hardness (ASTM 60 57 58 6763.00 61.00 63.50 65.00 D2240) Moisture Test using the 0.07 0.05 0.040.00111 0.00051 0.00057 Sartorius Moisture Analyzer (%) Ash Test (ASTMD5630- 15.4 14.46 14.44 0.1469 0.1369 0.1649 06) (%) ASTM D256 4.13410.42 10.194 2.785 3.1 3.8 4.4 5.5 Impact Resistance (ft-lbf/in) ASTMD256 10.334 26.05 25.485 6.961 7.7 9.5 11.0 13.7 Impact Strength(ft-lbf/in2) ASTM D638 3,170 2,668 2,538 3,115 3,043 2,747 3,341 3,410Type 4 Rigid Tensile Strength Stress Yield (psi) 3 in/min. B ASTM D638161,003 113,403 107,044 169,996 153,696 109,262 166,017 171,920 Type 4Rigid Tensile Modulus Youngs Modulus (psi)3in/min ASTM D790 1,492 1,1851,073 1,878 1,460 1,065 1,474 1,508 Flexural Strength Bending Strength @Peak (lbf/in2) ASTM D790 73,116 56,812 83,929 90,296 Flexural ModulusBending Modulus (lbf/in2) Specific Gravity 1.046 1.041 1.041 0.9 1.0420.941 1.038 1.057 ASTM D792 Shore D Hardness (ASTM 60 57 58 67 63.0061.00 63.50 65.00 D2240) Moisture Test using the 0.07 0.05 0.04 0.001110.00051 0.00057 Sartorius Moisture Analyzer (%) Ash Test (ASTM D 15.414.46 14.44 0.1469 0.1369 0.1649 5630-06) C ASTM D256 4.134 10.42 10.1942.785 3.1 3.8 4.4 5.5 Impact Resistance (ft-lbf/in) ASTM D256 10.33426.05 25.485 6.961 7.7 9.5 11.0 13.7 Impact Strength (ft-lbf/in2) ASTMD638 3,170 2,668 2,538 3,115 3,043 2,747 3,341 3,410 Type 4 RigidTensile Strength Stress Yield (psi) 3 in/min. ASTM D638 161,003 113,403107,044 169,996 153,696 109,262 166,017 171,920 Type 4 Rigid TensileModulus Youngs Modulus (psi) 3 in/min ASTM D790 1,492 1,185 1,073 1,8781,460 1,065 1,474 1,508 Flexural Strength Bending Strength @ Peak(lbf/in2) ASTM D790 73,116 56,812 83,929 90,296 Flexural Modulus BendingModulus (lbf/in2)

TABLE 13 Example 9 10 11 12 13 14 15 16 A Specific 1.044 1.045 1.0431.046 1.033 1.039 1.04 1.04 Gravity ASTM D792 Shore D 65.00 65.50 63.5064.50 60.50 60.50 62.00 64.00 Hardness (ASTM D2240) Moisture Test0.00064 0.0006 0.00057 0.00058 0.00085 0.00071 0.00072 using theSartorius Moisture Analyzer (%) Ash Test 0.1476 0.14832 0.1511 0.15110.1474 0.1488 0.1516 0.15006 (ASTM D 5630-06) (%) ASTM D256 6.6 6.7 7.68.5 10.0 10.4 11.1 11.1 Impact Resistance (ft-lbf/in) ASTM D256 16.516.9 19.0 21.4 24.9 26.0 27.8 27.8 Impact Strength (ft-lbf/in2) ASTMD638 3,285 3,317 3,054 3,132 2,492 2,454 2,316 2,763 Type 4 RigidTensile Strength Stress Yield (psi) 3 in/min. B ASTM D638 145,768151,451 151,654 146,727 110,801 105,660 100,193 104,278 Type 4 RigidTensile Modulus Youngs Modulus (psi) 3 in/min ASTM D790 1,436 1,4921,432 1,504 987 948 1,053 1,298 Flexural Strength Bending Strength @Peak (lbf/in2) ASTM D790 75,780 80,856 75,903 83,487 49,808 45,07558,547 73,307 Flexural Modulus Bending Modulus (lbf/in2)

TABLE 14 Example 17 18 19 20 21 I 22 23 A Specific Gravity 1.041 1.0431.043 1.04 1.041 0.952 1.053 1.045 ASTM D792 Shore D Hardness 63.5063.50 63.50 63.50 63.0 66.0 66.5 63.0 (ASTM D2240) Moisture Test usingthe 0.00053 0.00054 0.00053 .059 0.052 0.073 Sartorius Moisture Analyzer(%) Ash Test (ASTM D 0.15033 0.14896 0.15248 0.15049 15.10 15.415630-06) (%) ASTM D256 11.1 11.2 11.3 11.5 11.339 1.802 3.661 4.638Impact Resistance (ft-lbf/in) ASTM D256 27.8 28.0 28.3 28.7 28.348 4.5059.153 11.596 Impact Strength (ft-lbf/in2) ASTM D638 2,678 2,811 2,7402,630 2,799 3,690 3,700 2,747 Type 4 Rigid Tensile Strength Stress Yield(psi) 3 in/min. B ASTM D638 122,069 125,751 114,216 118,269 128,758185,426 197,707 131,392 Type 4 Rigid Tensile Modulus Youngs Modulus(psi) 3 in/min ASTM D790 1,178 1,297 1,307 1,256 1,547 1,335 1,764 1.247Flexural Strength Bending Strength @ Peak (lbf/in2) ASTM D790 64,58071,370 73,375 69,906 93,949 68,521 96,255 66,698 Flexural ModulusBending Modulus (lbf/in2)

TABLE 15 Example 24 25 26 27 J 28 29 K A Specific Gravity 1.051 1.0481.041 1.052 0.951 1.048 1.041 1.047 ASTM D792 Shore D Hardness 66.0 66.063.0 67.0 65.5 66.5 63.0 66.0 (ASTM D2240) Moisture Test using 0.0260.063 0.057 0.056 0.081 0.109 0.069 the Sartorius Moisture Analyzer (%)Ash Test (ASTM D 14.99 14.9 14.98 14.93 14.99 15.24 15.35 5630-06) (%)ASTM D256 3.275 6.013 8.619 4.719 1.574 2.941 4.143 1.470 ImpactResistance (ft-lbf/in) ASTM D256 8.188 15.034 21.547 11.799 3.934 7.35410.357 3.675 Impact Strength (ft-lbf/in2) ASTM D638 3,603 3,555 2,7853,825 3,422 3,638 2,681 3,435 Type 4 Rigid Tensile Strength Stress Yield(psi) 3 in/min. B ASTM D638 186,997 170,833 126,141 195,469 145,813184,519 120,988 184,971 Type 4 Rigid Tensile Modulus Youngs Modulus(psi) 3 in/min ASTM D790 1,770 1,619 1,184 1,748 1,234 1,574 1,182 1,582Flexural Strength Bending Strength @ Peak (lbf/in2) ASTM D790 91,03491,490 64,685 100,975 70,815 78,980 63,829 78,820 Flexural ModulusBending Modulus (lbf/in2)

TABLE 16 Example 30 31 32 33 34 35 36 37 A Specific Gravity 1.051 1.0421.049 1.046 1.038 1.046 1.045 1.04 ASTM D792 Shore D Hardness 66.5 62.567.0 65.0 65.0 65.0 65.0 66.5 (ASTM D2240) Moisture Test using 0.0450.085 0.06 0.085 0.059 0.079 0.075 0.069 the Sartorius Moisture Analyzer(%) Ash Test (ASTM D 15.13 14.93 14.01 14.49 14.49 15.08 14.38 13.295630-06) (%) ASTM D256 4.017 7.083 3.020 3.277 7.033 5.000 4.842 4.026Impact Resistance (ft-lbf/in) ASTM D256 10.042 17.708 7.549 8.192 17.58212.500 12.105 10.065 Impact Strength (ft-lbf/in2) ASTM D638 3,213 2,5603,485 3,577 2,679 3,036 3,121 3,467 Type 4 Rigid Tensile Strength StressYield (psi) 3 in/min. B ASTM D638 166,360 112,958 180,705 175,340121,650 143,340 153,177 160,210 Type 4 Rigid Tensile Modulus YoungsModulus (psi) 3 in/min ASTM D790 1,402 1,117 1,670 1,636 1,126 1,4041,400 1,542 Flexural Strength Bending Strength @ Peak (lbf/in2) ASTMD790 73,684 59,693 90,569 89,352 61,172 79,305 80,941 87,366 FlexuralModulus Bending Modulus (lbf/in2)

TABLE 17 Example 38 39 40 41 42 L 43 44 A Specific Gravity 1.044 1.0431.053 1.043 1.049 0.941 0.993 1.018 ASTM D792 Shore D Hardness 65.0 64.567.0 65.0 65.0 61.0 61.0 62.0 (ASTM D2240) Moisture Test using 0.0950.084 0.065 0.124 0.066 0.071 0.052 the Sartorius Moisture Analyzer (%)Ash Test (ASTM D 14.95 14.8 15.52 15.47 15.21 7.602 11.128 5630-06) (%)ASTM D256 5.355 5.544 3.515 5.032 5.138 4.089 5.352 5.394 ImpactResistance (ft-lbf/in) ASTM D256 13.389 13.859 8.787 12.580 12.84410.222 13.271 13.485 Impact Strength (ft-lbf/in2) ASTM D638 3,008 2,9203,504 3,060 3,007 2,645 3,153 3,173 Type 4 Rigid Tensile Strength StressYield (psi) 3 in/min. B ASTM D638 138,141 130,066 173,560 144,469142,682 99,019 143,529 156,459 Type 4 Rigid Tensile Modulus YoungsModulus (psi) 3 in/min ASTM D790 1,340 1,040 1,728 1,393 1,395 1,6901,825 1,878 Flexural Strength Bending Strength @ Peak (lbf/in2) ASTMD790 75,812 63,103 96,380 79,018 78,936 104,171 115,608 117,979 FlexuralModulus Bending Modulus (lbf/in2) ASTM ASTM D 161.0 156.6 149.2 3418-08Thermal Capacity (J/g)

TABLE 18 Example 45 46 47 48 49 50 51 52 A Specific Gravity 1.048 1.0751.107 0.986 1.014 1.041 1.069 1.102 ASTM D792 Shore D Hardness 61.0 62.062.0 60.0 60.0 60.0 61.0 61.0 (ASTM D2240) Moisture Test using the 0.0730.043 0.041 0.04 0.072 0.058 0.042 0.066 Sartorius Moisture Analyzer (%)Ash Test (ASTM D 15.07 18.662 22.466 7.313 11.038 14.931 18.693 22.285630-06) (%) ASTM D256 5.376 5.696 6.019 9.020 9.337 10.071 11.54011.857 Impact Resistance (ft- lbf/in) ASTM D256 13.440 14.239 15.04722.549 23.341 25.177 28.850 29.642 Impact Strength (ft- lbf/in2) ASTMD638 3,261 3,251 3,158 2,676 2,790 2,838 2,781 2,792 Type 4 RigidTensile Strength Stress Yield B ASTM D638 166,738 171,372 171,462117,701 126,236 138,884 139,836 146,688 Type 4 Rigid Tensile ModulusYoungs Modulus (psi) 3 in/min ASTM D790 1,908 1,913 2,024 1,541 1,5221,539 1,570 1,683 Flexural Strength Bending Strength @ Peak (lbf/in2)ASTM D790 123,467 123,061 127,889 94,911 94,151 95,090 95,975 103,072Flexural Modulus Bending Modulus (lbf/in2) ASTM D 3418-08 145.6 139.1111.4 128.9 132.0 118.1 113.9 111.4 Thermal Capacity (J/g)

TABLE 19 Example 52A 52B 52C 52D 52E R S T A Specific Gravity 0.9931.015 1.043 1.071 1.103 0.948 0.945 0.943 ASTM D792 Shore D Hardness62.0 62.0 62.0 62.0 52.0 59.0 60.0 63.0 (ASTM D2240) Moisture Test usingthe 0.072 0.059 0.052 0.06 0.063 Sartorius Moisture Analyzer (%) AshTest (ASTM 5630- 7.01 10.9 15.08 18.59 22.11 06) (%) ASTM D256 2.5012.317 2.354 2.343 2.511 13.257 12.496 4.061 Impact Resistance (ft-lbf/in) ASTM D256 6.251 5.792 5.880 5.859 6.277 33.141 31.241 10.152Impact Strength (ft- lbf/in2) ASTM D638 2,805 2,831 2,962 2,949 3,0113,705 3,397 2,728 Type 4 Rigid Tensile Strength Stress Yield B ASTM D638124,324 135,403 145,902 154,735 155,485 168,878 147,277 102,559 Type 4Rigid Tensile Modulus Youngs Modulus (psi) 3 in/min ASTM D790 1,7091,735 1,822 1,938 1,917 2,003 1,883 1,600 Flexural Strength BendingStrength @ Peak (lbf/in2) ASTM D790 106,118 107,901 114,928 123,498122,901 125,487 112,637 98,233 Flexural Modulus Bending Modulus(lbf/in2) ASTM ASTM D 3418- 153.9 141.8 137.9 135.9 126.7 187.1 171.9158.8 08 Thermal Capacity (J/g)

TABLE 20 Example 53 54 55 56 57 58 59 60 A Specific Gravity 1.122 1.1511.186 1.220 1.259 1.302 1.117 1.144 ASTM D792 Shore D Hardness 66.0 67.067.0 67.5 68.0 68.5 64.5 65.0 (ASTM D2240) Moisture Test using the 0.0580.041 0.065 0.172 0.064 0.038 0.055 0.076 Sartorius Moisture Analyzer(%) Ash Test (ASTM 5630- 24.42 27.83 31.44 34.9 38.56 41.98 24.18 27.6806) (%) ASTM D256 7.386 6.223 5.127 4.264 3.774 3.562 12.036 12.283Impact Resistance (ft- lbf/in) ASTM D256 18.465 15.559 12.817 10.6609.436 8.906 30.091 30.707 Impact Strength (ft- lbf/in2) ASTM D638 3,4333,366 3,400 3,445 3,316 3,311 2,827 2,854 Type 4 Rigid Tensile StrengthStress Yield (psi) 3 in/min. B ASTM D638 185,079 188,037 196,158 210,682205,858 201,092 143,009 152,751 Type 4 Rigid Tensile Modulus YoungsModulus (psi) 3 in/min ASTM D790 2,054 2,067 2,157 2,199 2,243 2,2721,663 1,664 Flexural Strength Bending Strength @ Peak (lbf/in2) ASTMD790 130,494 135,567 145,871 146,959 151,544 150,756 103,797 104,314Flexural Modulus Bending Modulus (lbf/in2) ASTM ASTM D 3418- 124.7 118.0112.5 108.7 103.5 94.6 102.8 94.9 08 Thermal Capacity (J/g)

TABLE 21A Example 61 62 63 64 Specific Gravity 1.175 1.214 1.254 1.295ASTM D792 Shore D Hardness 65.0 65.5 65.5 66.0 (ASTM D2240) MoistureTest using the 0.051 0.066 0.067 0.0972 Sartorius Moisture Analyzer (%)Ash Test (ASTM D 31.27 34.73 38.22 41.81 5630-06) (%) ASTM D256 11.5199.304 8.387 7.154 Impact Resistance (ft- lbf/in) ASTM D256 28.797 23.26020.967 17.884 Impact Strength (ft- lbf/in2)

Samples or Examples 52 A through 52E demonstrate the ability to createcompositions that use fractional melt resin with Masterbatch V inamounts ranging from about 10% to about 33%. Impact resistance remainedrelatively constant at amounts less than 3, greater than ComparativeExamples B and C and samples 1A and 1 B, which used differentmasterbatches than preferred Masterbatch V, but much less than Examples43-47 which used the fractional melt resin along with Masterbatch V inthe same range of amounts.

Comparative Examples R, S, and T demonstrate the physical properties ofthe preferred fractional melt resins in neat form and the preferredthermoplastic matrix resin also in neat form, respectively. The impactresistances of the two fractional melt resins were greater than anycomposite achieved but lacked the other physical properties to be usefulbecause they are not suitable for use in an injection molding process.Comparative Example T can be compared to Comparative Examples A, F, H,and L, all 100% ExxonMobil 6605.70 HDPE. The impact resistances are veryclose in measurement among them, providing a basis of comparison for thevarious sets of experiments comprising the Examples.

Examples 53-58 show the use of increasing amounts of the preferredMasterbatch V with slightly decreasing amounts of preferred fractionalmelt resin and significantly decreasing amounts of ExxonMobil 6605.70HDPE. The impact resistances decreased as Masterbatch V contentincreased, but all remained above the level of 2.8.

Examples 59-64 illustrate that result when the fractional melt resin isevenly split between Marlex HHM 5502BN HDPE and Westlake EN1807AA HDPEfractional melt resins. Each of Examples 59-64 can be compared withExamples 53-58 to determine that the blend of the two differentfractional melt resins can increase the impact resistances of thecompositions, all other factors constant.

Examples 59-61 all had impact resistances within 86% of the impactresistance of Marlex HHM 5502BN HDPE alone (Comparative Example R) withMasterbatch V content of 35, 40, and 45 weight percent respectively, allother factors constant. Unexpectedly, the impact resistance of Example60 (40 weight percent of Masterbatch V) was greater than the impactresistances of Examples 59 and 61, indicating a preference for Example60, all other factors constant.

It should be noted that in many of the compositions herein discussed,fractional melt materials were used. Fractional melt material has a meltflow index of less than one. However, it should be understood that lowmelt index materials may also be used in lieu of or with the fractionalmelt material. Low melt index materials have a melt flow index of aboutless than three.

Turning now to FIGS. 2-8, they are all photomicrographs at 5000magnification of Comparative Examples A, B 7, 6, 8, 21, and 20,respectively. FIG. 2 is a photo of Example A which is ExxonMobil 6605.70HDPE. It provides a visual image of the thermoplastic base resin againstwhich other samples may be compared. FIG. 3 shows Composition B which isa combination of Masterbatch I and the ExxonMobil 6605.70 HDPE. In FIG.2, the fly ash particles are resident in but dissociated from sockets ofthermoplastic base resin.

FIG. 4 is an image taken of Example 7 and illustrates the unexpectedbenefits of using Masterbatch IV in forming a composition in comparisonto compositions formed using Masterbatch III. That is, in Masterbatch IVwe see that an increased amount of fractional melt resin along with thedecreased amounts of compatibilizer and oil-softened styrenic blockcopolymer yield a product 46 in which fly ash particles are submergedbeneath the fractured surface of base resin.

FIG. 5 shows Example 6 (Table 3) which can be compared to FIG. 4 thatshows Example 7 in that the ingredient formulations are the same.However, Example 6 did not employ a masterbatch. The slightly lowerimpact resistance of Example 6 compared with Example 7 was alsonoticeable in FIG. 5 in comparison to FIG. 4. It is believed that thelower impact resistance is related to exposed fly ash particles in baseresin sockets with a few tendon connections between particles andsocket.

Turning now to FIG. 6, it is an enlarged image of Example 8. It showsfly ash particles with a combination of compatibilizer likecompatibilizer 36, fractional melt resin 60, blend 54 of oil-softenedstyrenic block copolymer 52 and mineral oil 50 in the ExxonMobil 6605.70HDPE base resin 42. FIG. 6 shows the tendon connection of fly ashparticles to the combination.

FIG. 7 is an image of Example 21 which is a combination of Masterbatch Valong with Exxon Mobil 6605 as a base resin 42 with Marlex 5202 andWestlake EN 1807AA as fractional melt resins as shown in Table 5. FIG. 7shows enhanced tendon connections in comparison to those seen in FIG. 6.The two fly ash particles are intimately and repeatedly connected to thebase resin by the many tendons between the particles and resin.

FIG. 8 illustrates Example 20 which is a combination of Masterbatch VIalong with Exxon Mobil 6605 as a base resin 42 with Marlex 5502 andWestlake EN 1807AA as fractional melt resins as shown in Table 5. FIG. 8shows further enhanced tendon connections and in turn is an unexpectedimprovement upon the Examples 6-8 and 21. Use of Masterbatch VI with acombination of fractional melt resin evenly split between Marlex HHM5502BN HDPE and Westlake EN1807AA HDPE resulted in a cross-sectionalfractional view of no fly ash particles, even though they are present ata 15 weight percent loading. The reason fly ash particles are absentfrom view was because the base resin suffered cohesive failure beforethe interface between fly ash particles and base resin and a combinationof compatibilizer, fractional melt resin, and oil-softened styrenicblock copolymer suffered adhesive failure. In other words, the bondbetween the fly ash particles and the surrounding resin(s) was greaterthan the resin(s) themselves. Therefore, one can expect the formulationsof any of the Examples having measured impact resistances of at leastabout 11 to have greater adhesive strength between fly ash particles andresin(s) than the cohesive strength of the resin(s) alone.

Sample or Example 20 is a combination that produces a bond between thefly ash particles and the resin material that results on an impactresistance that is substantially enhanced over the impact resistance ofthe resin by itself. FIG. 8 supports or shows the strength of the bondbecause the particles are not visible and further supports a belief thatthe sample, produced as stated, is believed to result in the substantialcoating of the fly ash particles with the base resin and a combinationof compatibilizer, fractional melt resin, and oil-softened styrenicblock copolymer. That is, it is presently believed that the fly ashparticles are totally encapsulated. Further, it is believed thatcompositions that result in the immobilization of fly ash particlesproduce enhanced impact resistance. The immobilization is apparent in atleast FIGS. 6, 8, 21, and 20 in comparison to FIG. 3 showing thedissociated and loose fly ash particles in the larger resinous sockets.

As noted before, it is believed that the addition of a blowing agent 16into the filter blend 18 in the process of preparing the composition 44or the introduction of the agent 16 via line 15 into the mixture 47 asit is being heated as it is about to be formed into a product or objectwill yield a final product 46 that is less dense. That is, the blowingagent 16 will release gas into the composition 44 or material 17 as theblowing agent heats up to form a product that is like honey comb in thatit has a substantial plurality of voids, spaces and/or pockets in thefinal product but still has a smooth exterior surface for the product.

TABLE 22 Masterbatch Materials Ingredients VII VIII Eclipse Fly AshBlend B 70 70 (Revolutionary Plastics, Las Vegas, NV) Hydrotalcite acidscavenger 0.35 0.35 Chemtura Anox NDB 0.245 0.245 antioxidant ChemturaAlkanox antioxidant 0.245 0.245 Chemtura PolyBond 3009 5 maleatedpolyethylene (0.95 Density; 3-6 g/10 min. MFI) Chemtura PolyBond 3200 5maleated polypropylene (0.91 Density; 115 g/10 min. MFI) Kuraray Septon4033 SBC 4.5 4.5 Flakes Sonneborn 550 Mineral Oil 0.5 0.5 Chevron MarlexHMN ® TR- 19.16 935 MDPE (0.936 Density; 6.0 MFI) Marlex 9708 HDPE(0.962 19.16 Density; 8.0 MFI) Total 100 100

TABLE 23 Example (Wt. %) U 65 66 67 68 69 A ExxonMobil 100 66.5 61.556.5 51.5 46.5 6605.70 HDPE (0.948 Density; 5 g/ 10 min MFI) Westlake 014.25 14.25 14.25 14.25 14.25 EN1807AAMarlex HHM 5502BN HDPE (0.921955Density; 0.735 g/10 min. MFI) Masterbatch 0 14.25 14.25 14.25 14.2514.25 VIIWestlake EN1807AA HDPE (0.921 Density; 0.7 g/10 min. MFI)Masterbatch VII 0 5 10 15 20 25 Total 100 100 100 100 100 100 TestDescription Physical Properties Specific Gravity 0.94 0.96 0.99 1.011.04 1.06 B Shore D 63.5 63.5 63.5 63.5 64 63.5 Durometer using ASTMD2240 Notched Izod Impact Properties (ASTM D256) Notched IZOD 3.36 13.3513 12.58 12.29 12.49 Impact Resistance (ft-lbf/in) Notched IZOD 8.3933.38 32.51 31.45 30.72 31.24 Impact Strength (ft-lbf/in²) TensileProperties (ASTM D638 Type 4 Rigid) Tensile Strength 2,850 3,282 3,1453,080 2,860 2,742 Stress Yield (psi)² in/min. Tensile Modulus 98,417107,267 104,841 114,686 109,642 98,313 Youngs Modulus (psi)² in/min CFlexural Properties (ASTM D790) Flexural Strength 1,857 1,639 1,6441,703 1,692 1,713 Bending Strength @ Peak (lbf/in²) Flexural Modulus114,632 99,281 102,069 104,880 103,211 104,281 Bending Modulus (lbf/in²)Injection Pressure Ave. Peak 0 0 0 2,014 2,022 2,018 Injection PressureDSC - J/g 153.7 108.4 120.1 115.8 111.9 108 Example (Wt. %) 70 71 72 7374 A ExxonMobil 41.5 36.5 31.5 26.5 21.5 6605.70 HDPE (0.948 Density; 5g/ 10 min MFI) Westlake 14.25 14.25 14.25 14.25 14.25 EN1807AAMarlex HHM5502BN HDPE (0.921955 Density; 0.735 g/10 min. MFI) Masterbatch 14.2514.25 14.25 14.25 14.25 VIIWestlake EN1807AA HDPE (0.921 Density; 0.7g/10 min. MFI) Masterbatch VII 30 35 40 45 50 Total 100 100 100 100 100Test Description Physical Properties Specific Gravity 1.11 1.13 1.151.21 1.23 B Shore D 65 65 65 66 66 Durometer using ASTM D2240 NotchedIzod Impact Properties (ASTM D256) Notched IZOD 10.98 10.2 9.71 8.557.94 Impact Resistance (ft-lbf/in) Notched IZOD 27.46 25.51 24.27 21.3819.84 Impact Strength (ft-lbf/in²) Tensile Properties (ASTM D638 Type 4Rigid) Tensile Strength 2,781 2,708 2,711 2,671 2,593 Stress Yield(psi)² in/min. Tensile Modulus 108,333 110,233 110,085 115,473 110,249Youngs Modulus (psi)² in/min C Flexural Properties (ASTM D790) FlexuralStrength 1,684 1,781 1,824 1,884 1,917 Bending Strength @ Peak (lbf/in²)Flexural Modulus 103,200 107,023 115,668 120,187 121,061 Bending Modulus(lbf/in²) Injection Pressure Ave. Peak 1,996 1,933 1,955 1,917 1,872Injection Pressure DSC - J/g 99.6 95.7 91.1 81.5 74.8

TABLE 24 Example (Wt. %) V 75 76 77 78 79 80 81 82 83 84 A Chevron 9005100 66.5 61.5 56.5 51.5 46.5 41.5 36.5 31.5 26.5 21.5 HDPE (0.945Density; 6.0 g/10 min MFI) Westlake 0 14.25 14.25 14.25 14.25 14.2514.25 14.25 14.25 14.25 14.25 EN1807AA- Marlex HHM 5502BN HDPE (0.921955Density; 0.735 g/ 10 min. MFI) Masterbatch 0 14.25 14.25 14.25 14.2514.25 14.25 14.25 14.25 14.25 14.25 VIIWestlake EN1807AA HDPE (0.921Density; 0.7 g/10 min. MFI) Masterbatch VII 0 5 10 15 20 25 30 35 40 4550 Total 100 100 100 100 100 100 100 100 100 100 100 Test DescriptionPhysical Properties Specific Gravity 0.94 0.96 0.98 1.01 1.04 1.06 1.11.12 1.15 1.18 1.24 Shore D 62 62.5 63 63 64 64 64.5 64.5 65 65 65.5 BNotched Izod Impact Properties (ASTM D256) Notched IZOD 8.85 14.38 14.3913.74 13.1 12.52 11.82 11.45 10.17 9.46 9.31 Impact Resistance(ft-lbf/in) Notched IZOD 22.12 35.96 35.97 34.34 32.76 31.3 29.55 28.6125.43 23.65 23.27 Impact Strength (ft-lbf/in²) Tensile Properties (ASTMD638 Type 4 Rigid) Tensile Strength 2,306 2,609 2,548 2,597 2,608 2,6172,623 2,621 2,559 2,563 2,491 Stress Yield (psi)² in/min. TensileModulus 69,346 91,642 87,727 86,527 91,015 93,044 106,457 101,440110,741 128,217 116,353 Youngs Modulus (psi)² in/min Flexural Properties(ASTM D790) Flexural Strength 1,526 1,474 1,537 1,540 1,597 1,627 1,7191,700 1,785 1,800 1,909 Bending Strength @ Peak (lbf/in²) FlexuralModulus 93,404 89,935 93,755 92,044 96,809 97,804 104,366 101,562108,104 108,673 121,298 Bending Modulus (lbf/in²) C Injection PressureAvg. Peak (lb/in²) 2,109 2,023 2,051 2,065 2,088 2,005 2,002 1,961 1,9541,955 1,898 Injection Pressure DSC J/g* 124.8 115.6 111.1 108.6 102.3101.1 94.9 92.1 88.1 83.7 77.6 *Differential Scanning CalorimetryJoules/gram

TABLE 25 Example (Wt. %) W 85 X 86 Y 87 Z 88 A Chevron ALN-070 “NoBreak” 100 50 Polypropylene Copolymer (0.9 Density; 7 MFI) Generic “NoBreak” 100 50 Polypropylene Copolymer (11 MFI) Flint Hills AP7310-HS “No100 50 Break” Polypropylene Copolymer (0.9 Density; 10 MFI) B CPPP.1220GBLACK “No 100 50 Break” Polypropylene Copolymer (9.5-11.0 MFI)distributed by PolyOne Corporation Masterbatch VIII 21.5 21.5 21.5 21.5Marlex HHM 5502BN HDPE 28.5 28.5 28.5 28.5 (0.955 Density; 0.35 g/10min. MFI) Total 100 100 100 100 100 100 100 100 Notched Izod ImpactProperties (ASTM D256) Impact Resistance (ft-lbf/in) 3 7 3 7.7 2.6 4.92.5 4.1 Impact Strength (ft-lbf/in²) 7.6 17.5 7.4 19.2 6.5 12.1 6.1 10.3C Tensile Properties (ASTM D638 Type 4 Rigid) Tensile Strength StressYield 3,108 3,013 3,211 3,072 3,143 3,364 2,946 3,368 (psi)² in/min.Tensile Modulus Youngs 157,750 161,864 159,950 157,803 152,709 176,717142,659 169,810 Modulus (psi)² in/min Flexural Properties (ASTM D790)Flexural Strength Bending 2,874 2,345 2,610 2,093 2,351 2,361 2,3782,367 Strength @ Peak (lbf/in²) Flexural Modulus Bending 148,468 134,700136,692 122,047 124,915 138,151 126,079 138,552 Modulus (lbf/in²)

Examples 65-74 identify alternative embodiments in which the fractionalmelt is not included or mixed with the masterbatch material but ratherwith to the final formulation being molded. That is, the Masterbatch VIIis mixed with the factional melt material and another resin as it isready to be heated and molded. For Examples 65-74, two differentfractional melt resins were used and kept at a constant weight percent,with the conventional higher melt flow resin and Masterbatch VIIdecreasing and increasing in tandem, respectively.

Table 23 demonstrates the truly unexpected result that Notched Izodimpact resistance is maximized with the minimum amount of usage ofmasterbatch. However, even at 50 weight percent usage, Notched Izodimpact resistance is more than double the amount of the neat higher meltflow resin. Also, though specific gravity trends upward, the Shore Dhardness remains relatively constant. Finally, tensile and flexuralmoduli are relatively consistent across the range of increased amount ofmasterbatch and fractional melt resin in Examples 65-74, but time toonset of crystallization as measured by DSC in Joules/gram demonstratesa significant and unexpected improvement in nucleation of those Examples65-74 over the neat resin of Comparative Example U. Moreover, a fasteronset to crystallization can improve cycle time of molding plasticarticles sequentially made from compounds disclosed. From the aboveincluding Table 23, it can be seen that one can tailor formulations ofthe present invention as demonstrated in Examples 65-74 into any moldedplastic article having nearly any desired combination of impactresistance, tensile modulus, flexural modulus, and other structuralcharacteristics, using the three component combination of neat resin,fractional melt resin(s), and masterbatch containing an effective amountof maleated polyethylene.

Table 24 essentially confirms the results of Table 23, except using adifferent conventional higher melt flow polyethylene resin, commerciallyavailable and often used in the molding of plastic articles. Examples75-84 progress with increasing amounts of masterbatch over theconventional resin of Comparative Example V with similar unexpectedresults as seen for Examples 65-74. Again, two different fractional meltresins were used, and their weight percents were held constant for theseexperiments. Table 24 therefore demonstrates the robustness of thepresent invention based on the use of a different conventionalpolyethylene resin than used in the Examples 65-74 shown in Table 23.

Table 25 is organized to show a shift from 100% neat resin of differentmelt flow grades of four polypropylene copolymers to 50% of those neatresins, respectively with about 22% of Masterbatch VIII (containing amaleated polypropylene) and about 28% fractional melt resin added. Themixtures and the performance of the compositions using the MasterbatchVIII remain essentially constant in amount across the four Examples85-88. Significantly, and unexpectedly, there was no incompatibilitynoted in the blending of a fractional melt high density polyethylene ora polyethylene carrier in Masterbatch VIII with a polypropylenecopolymer. Generally, Table 25 demonstrates that one can replace as muchas 50% polypropylene copolymer “no break” resin with the combination offractional melt HDPE and masterbatch having HDPE masterbatch carrier andmaleated polypropylene without adverse affecting the physical propertiesof the conventional neat resin. Moreover, unexpectedly, one can actuallyimprove the physical properties of impact resistance in every instancefor every melt flow grade tested.

When comparing performance results in Tables 23, 24 and 25, other thanflexural modulus which decreased slightly, all other physical propertiesmeasured were relatively consistent between the Comparative Examplewithout the fractional melt resin and the masterbatch. As with apolyethylene resin explored in Tables 23 and 24, the comparison betweenComparative Examples W-Z and Examples 85-88, respectively, teach thatone is able to utilize the fractional melt polyethylene resin and themasterbatch containing a maleated polypropylene with a polypropylenecopolymer “no break” resin to achieve increased impact resistancewithout deleterious change to other physical properties.

From Tables 23-25, it can be seen that one can use fly ash withpolyethylene in an amount as little as 3.5 weight % (Examples 65 and 75)and as much as 35 weight % (Examples 74 and 84) in order to achievesuperior physical properties over the same polyethylene alone,particularly impact resistance, if fractional melt resin is alsopresent. The masterbatch formulation, such as Masterbatch VII,significantly contains maleated polyethylene, as used in priorembodiments, to achieve superior impact resistance.

Significantly, these Examples 65-84 demonstrate that the fractional meltresin(s) need not be in the masterbatch in order to obtain thesesuperior results. Therefore, it is possible to have both the benefits ofa masterbatch easier to make because of the absence of the less flowingfractional melt resin(s) and the benefits of a molded plastic articlebecause of the presence of the fractional melt resin(s). The moldingconditions unexpectedly are sufficiently tolerant of the fractional meltresin(s) being added without previous melt mixing with the otheringredients of the masterbatch. The use of two different fractional meltresins in Examples 65-84 demonstrate that neither fractional melt resinis disruptive to molding conditions.

Considering the trends from Examples 65 and 75 to Examples 74 and 84, itis quite unexpected that one can replace conventional higher melt flowpolyethylene resins (having a higher cost relative to fractional meltresins) with the combination of fractional melt resin(s) and masterbatchof the as disclosed to achieve improved and indeed superior impactresistance without loss of other physical properties. The superiorimpact resistance while maintaining consistent other physical propertiesas see in tables 23-25 is being achieved using only 21.5% ofconventional polyethylene resin remaining in Examples 74 and 84—a 79.5%reduction in content as compared with Comparative Examples U and V—isquite unexpected.

Examples 85-88 are of particular significance as they demonstrate that apolyethylene fractional melt resin can be used with a masterbatch thathas or uses fly ash (in a polyethylene carrier along with maleatedpolypropylene) in an amount of about 22 wt. % in polypropylene copolymerin order to achieve superior physical properties over the samepolypropylene. Notably there is significant improvement in impactresistance when fractional melt resin is also present.

Also significantly, as with the polyethylene Examples 65-84, thefractional melt resin need not be present in the masterbatch to achievethese results, allowing for a less complicated manufacture ofmasterbatch and a superior final plastic article.

It is contemplated that a series of examples for polypropylene copolymerusing the same progression as seen in Tables 23 and 24 for polyethylenewill yield similar results as seen in Tables 23 and 24 for polyethylenecopolymer.

Additional tests have demonstrated that one can reduce the amount ofPolybond® maleated polyolefin compatibilizer or oil-softened Septon®styrenic block copolymer from 5 weight percent to 1 or 2 weight percentand achieve acceptable Notched Izod impact resistance properties whencompared to the neat resin. These masterbatches, even though lessperforming when compared with Masterbatches VII and VIII in Table 22,are nonetheless commercially valuable when a similar impact resistanceproperty is desired for a plastic article using a less expensivemasterbatch, thus an overall less expensive compound, thereby producinga less expensive but fully functional molded plastic article.

Referring back to Table 22, the MasterBatch material VII shown is quitesimilar to MasterBatch VI except that it includes HDPE with a MFI of 8instead of a MDPE like Chevron TR 935 material. This Masterbatch VII isthen processed with a fractional melt like fractional melt 60 and baseresin like base resin 42 to form a mixture 47 into which one inserts oradds the blowing agent 16 via line 15 as the mixture 47 is being heatedand thereafter mechanically processed 48 into work product 46. Inmaterial with blowing agent formed as seen in Table 23, the hardness andother physical properties are expected to be better than the base resinsthat are seen in the tables 1-21 above.

The enhanced benefits from the combination of the blowing agent with acomposition having fly ash as the filler was not heretofore appreciated.Typically, the Blend B fly ash used in the formation of a Masterbatch ora composition as herein disclosed will have by count many more smallerparticles of fly ash than larger particles. It is believed that thesmaller particles (which are those less than 1 micron in effectivediameter) are about 95% of any given number while being by mass about 8%to 11% of mass of the fly ash of that volume. Thus, the larger particles(greater than 1 micron) are by mass about 90% of any given volume.Without being limited to a particular theory, it is presently believedthat the multiplicity of particle sizes dominated by the smallerparticles contributes to a reduced or lower viscosity during the meltphase leading to improved dispersion and distribution of the smallerparticles. At the same time, it is believed that the lower viscosityleads to enhanced flow characteristics so that less pressure is neededin processing (e.g., injection molding); and less energy (e.g.,electricity) is needed to process into a final product. Indeed,temperatures can be kept lower leading to further energy savings whilewear or erosion is minimized in relation to the use of more abrasiveparticles like gold.

FIG. 9 is a photograph of solid cured polyethylene material that hasBlend B added in a melt phase. The small dark spots of the typeidentified by the arrow show the good dispersion of the particles in thecomposition. The large number by count of the smaller particles arebelieved to aid in the nucleation of gas bubbles as the blowing agentconverts to a gas or is decomposing from its solid form to a gas form.More specifically, it is believed that the presence of the largequantity of the smaller filler particles leads to the formation of amaterial in which the pockets or bubbles are considerably smaller insize. That is, there is greater dispersion and in turn, finer (smallerin size) bubbles/pockets and more uniform distribution of thebubbles/pockets. Thus one may avoid use of supercritical carbon dioxideto aid in the formation of reduced cell sizes (e.g., less than 0.05micron) as taught by Zhai et al, Heterogeneous Nucleation UniformizingCell Size Distribution In Microcellular Nanocomposites Foams (BeijingNational Laboratory for Molecular Sciences, et al, available on theworld wide web at www.sciencedirection.com, 7 Sep. 2006).

There are reports that nano particles such as gold nanoparticles areused to change or improve properties of various compositions. NanoPartz™of Loveland, Colo. offers a line of such nano particles. But is believedthat the use of such particles is limited as it is believed that volumesof such nano particles in excess of 1% by weight lead to clumping andreduce advantages and change the flow properties. The use of aninorganic filler and more particularly the use of fly ash has avoidedthe problems and results in better dispersion and nucleation withenhanced flow characteristics as seen in FIG. 9.

It is also believed that the nucleation or size of the bubbles or holescan be controlled by using inorganic fillers such as fly ash withdifferent particle size distribution. That is, Blend B used to make theMasterbatch VII in Table 22 has particles that range from 200 nanometersup to 250 microns. Reducing the range of size from that used in Blend Bto, for example, 200 nanometers to about 10 microns or about 50 micronsis believed to reduce the cell structure or smaller and more holes orbubbles in the final cured composition while further reducing orcontrolling the viscosity and energy consumption during processing.

Turning now to FIG. 10, it is a photograph of a solid cured polyethyleneresin. It is made using Blend B but without a foaming agent or colorant.The particles are well dispersed or relatively evenly distributedthroughout the structure. This photograph shows the results of using aninorganic filler like fly ash with a particle size distribution having alarge percentage of small particles. Indeed, it is believed that thedistribution can be controlled by using an inorganic filler like fly ashin which more than 50% and up to 99% of the total particles are lessthan 1 micron in effective diameter.

FIGS. 11 and 12 are images of samples made in which 0.3225% of a blowingagent such as Baothr has been used. Baothr is an endothermic blowingagent in powder form available from PolyOne Corporation of Avon Lake,Ohio. In FIG. 11 the Baothr blowing agent was added into the MasterbatchVII with the HDPE reduced by that amount. Thereafter the Masterbatch VIIas modified was mixed with a base resin and processed using normalmanufacturing procedures resulting in the production of the sample. FromFIG. 11, it can be seen that the cell structure is regular withconsistent small cells throughout. The cell sizes are believed to rangefrom about 30-150 microns in effective diameter with the average as canbe best estimated at about 96.06 microns. That is, the addition of thefoaming agent into a masterbatch to be used with a base resin in thenormal manufacturing process was found to be viable and lead to desirednucleation and dispersion.

FIG. 12 shows with the 0.3225% Baothr foaming agent added to thecomposition of the Masterbatch like Masterbatch VII and a base resin inthe final mixing before mechanical processing (or at the throat of thepress or extruder) (e.g., injection molding) into a product. Whileadequate or sufficient nucleation is evident and adequate dispersion isapparent, it is clear that nucleation and dispersion is not as regularor as even as seen in FIG. 11. In FIG. 12, cell sizes were seen to rangefrom about 25 to about 300 microns.

To show the structural differences, FIG. 13 is a photograph enlarged orat a magnification of about 10× of a cross section from a structuralfoam tube (about ½ inch in diameter×5″ inch in length) made of highdensity polyethylene resin having a melt flow index of about 8 with ablowing agent but without a masterbatch made with Blend B. That is, thematerial of FIG. 13 does not include any fly ash and has a largeirregular cell structure. In turn the mechanical properties of theproduct will be inconsistent if not unacceptable. In comparison, FIG. 14is a photograph at the same magnification as FIG. 13 of a cross sectionfrom a structural foam tube (about ½ inch in diameter×5″ inch in length)of about the same size as that of FIG. 13. The tube of FIG. 14 is alsomade of the same high density polyethylene resin having a melt flowindex of about 8; but it now includes and is mixed with a masterbatchmade using Blend B (which includes fly ash) and with the same amount ofthe same blowing agent. In FIG. 14, a piece was cut off forming edge 80to show the interior 82 with excellent dispersion of small cells in theinterior and encapsulation of the particles of fl y ash while the tubeitself has a smooth exterior surface 84. The dispersion and in turn thecells are more evenly distributed and smaller cells leads to a productthat is more consistent with predictable preferred mechanicalproperties. With the use of a filler material such as fly ash, it hasalso been noted that the processing procedures are not adverselyaffected but rather enhanced because thermal conductivity has not beenreduced due to the formation of cells or holes in the material. Rather,it is believed that the fly ash contributes to or enhances thermalconductivity. Also, there is also a more rapid crystallization of thepolymer which is assumed to be due to the multiple nucleation sites fromthe many particles under 1 micron.

With the use of a masterbatch like Masterbatch VII, it should also beunderstood that compositions can be formed using fractional melt inaddition to the base resin. Fractional melt (especially in its recycledor reclaimed regrind form) is desired because it is understood to beless expensive than base resin or virgin resin. It can be used withMasterbatch VII without adversely affecting the processing. That is, theprocessing pressures and temperatures can remain about the same or evenlowered in some instances while processing pressures and temperatureswithout the use of an inorganic filler like fly ash are notably higher.As seen in Table 26, fractional melt is used to form a composition toproduce a product comparable to what is seen in FIG. 14. The amount offractional melt can vary from a nominal amount of 1% up to about 75% insome applications.

TABLE 26 Foamed Material Weight PerCent Material 28.5% Fractional Melt 49% Base Resin   1% Blowing Agent 21.5% Masterbatch 100 Total

In reference to the blowing agent, the type selected will vary based onthe process. For example, endothermic reactions may be preferred in someapplications and processes with exothermic reactions may be preferred inyet others. Endothermic reactions typically produce carbon dioxide (CO₂)to form and fill the holes in the material as it hardens. Nitrogen (N₂)is typically a gas from an exothermic reaction to form and fill theholes. Blowing agents of different types and kinds can be found byTypical blowing agents include, but are not limited to isocyanate mixedwith water, hydrazine, and sodium bicarbonate. Blowing Agents such asthe Foamazol™ line of foaming agents are available from BergenInternational of Hasbrouck Heights, N.J. LaxNess of Leverkusen, Germanyoffers a line of Genitron® powder blowing agents. Blowing agents mayimpact on other physical properties including flowability or rheologyduring processing. FIGS. 15-17 are photographs taken of the crosssection of the rod of FIG. 14 with an enlarging microscope. FIG. 15shows the cells or holes formed with relative even distribution and allsized in a range that is small. FIG. 16 is a photograph of the samecross section of FIG. 14 but enlarged to show the holes or cells as theyare dispersed. A large area in FIG. 16 shows a large cell perhaps formedbecause mixing was not thorough or complete. FIG. 17 is yet a furtherenlargement showing the relative uniform spherical shape of the cellswith the others materials relatively evenly mixed holding the hollowcells.

While the formulations set forth above involve the use of a fly ashfiller, it should be further understood that other compositions can beformulated using the basic teachings as set forth hereinbefore that donot include fly ash/and or cinders or any other filler.

That is, certain thermoplastic resins are selected to manufactureproducts that will exhibit desired physical properties. Some productsneed to be soft or flexible while others need to be tough and hard.Polyethylene and polypropylene are typically selected for products thatneed to have good impact resistance (toughness) and good tensile andflexural strength (stiffness). Such materials and their equivalents aretypically used without fillers or similar additives.

One example of unmodified thermoplastic resin is generally known as “nobreak” polypropylene copolymer. The compositions of the presentinvention can dramatically increase impact resistance with comparable orbetter tensile strength and flexural strength using a high densitypolyethylene (HDPE) thermoplastic resin which is less expensive than the“no break” polypropylene copolymer.

While the compositions being formed as disclosed in connection with FIG.1 may include a variety of fillers from sawdust to glass balls to flyash, it should be understood that compositions may be formed without anyfiller as well as compositions with any other filler acceptable toproduce a desired product with desired physical properties.

It should be understood that other additives 26 can be supplied to beblended 22 into resin with or without the filler. For example, colorantscould be added at this early stage as well as other dry materials thatmay be desirably mechanically mixed or blended. In some cases thecompatibilizer will be liquid silane. The amount of liquid silane usedis so small or limited that it can be added to the filler 24 withoutotherwise affecting the processing properties of the filler 24 or it canbe added to the composition without a filler.

A suitable mineral oil 50 is mixed with a high performance stryrenicblock copolymer 52. The resulting blend 54 softens and enhances theflowability of the composition 44 when in melt form as it is mixed 56while contributing to the strength and elasticity of the final product46. That is, the base resin 42 and the masterbatch 38 create acomposition in melt form that could wet the surfaces of the processingequipment and reduce the production cycle time or throughput time.Adding the blend 54 of the mineral oil 50 and the copolymer 52contributes to the flowability of the composition 44 and is alsobelieved to contribute to the toughness of the product 46. In practice,it has been found that SEPTON® 4033 flakes available from KurarayAmerica, Inc. of Houston, Tex. are particularly useful as the copolymer52. Hydrobite® 550 PO white mineral oil offered by Sonneborn, LLC ofMahwah, N.J. has been found to be particularly useful as the mineral oil50. In use, it has been found that the blend 54 is best when mixed in aratio of about nine units of copolymer 52 to one unit of oil 50. Othersimilar mineral oils such as Pemeco® Drakeol® mineral oil are alsobelieved to be suitable for use.

The scope of this disclosure is not limited to the above embodiments andsamples presented in the above Tables 1-21. The many Examples provideddemonstrate that fly ash can be presented as an acceptable filler 24 andused with different amounts and different types of the variousingredients to result in or produce a final product 46 that has selectedphysical properties. The combination of fly ash, fractional melt resin,compatibilizer, and a blend of oil-softened styrenic block copolymer,preferably in combination with resins to create a masterbatch that arefurther combined with base resins including fractional melt resins, areless expensive than base resins by themselves, easier to process andthus are better performing than known base resins alone and have betterphysical properties than base resins alone. Simply stated, the user canchose how to vary the ingredients to attain the desired better physicalproperties, and the user can make products that are less expensive withselected enhanced physical properties.

1. A composition comprising a blowing agent; at least one fly ash havinga plurality of ash particles; an acid scavenger; an anti oxidant; and apolymer resin.
 2. The composition of claim 1 wherein said fly ashincludes a plurality of ash particles at or less than about 1 micron ineffective diameter.
 3. The composition of claim 2 wherein at least about70% of said fly ash are ash particles less than about 1 micron ineffective diameter by number.
 4. A composition comprising a couplingagent; a blowing agent; at least one fly ash having a plurality of ashparticles; an acid scavenger; an anti oxidant; a maleic anhydridegrafted high carrier resin having a melt flow index selected toencapsulate a plurality of ash particles; and a base resin.
 5. Thecomposition of claim 4 wherein said coupling agent, said blowing agent,said at least one fly ash, said acid scavenger, said anti oxidant, saidmaleic anhydride grafted high carrier resin are all combined to form amasterbatch and wherein said composition further includes a blend ofmineral oil mixed with SEPTON®4033 flakes, said blend being mixed intoone of the masterbatch and the base resin.
 6. The composition of claim 5further including an impact modifier.
 7. The composition of claim 6further including a low melt resin mixed in with said base resin andincluding a fractional melt resin.
 8. A composition comprising: fromabout 0.25 percent by weight to about 70 percent by weight of amasterbatch, said masterbatch being formed from about 1 percent to about95 percent by weight of a blend of at least one fly ash, about 0.1percent to about 2.0 percent by weight of an acid scavenger; about 0.1percent to about 4.5 percent by weight of an antioxidant, about 0.1percent to about 15 percent by weight of a coupling agent, about 1percent to about 70 percent by weight of a maleic anhydride modifiedhigh density polyethylene; and wherein said masterbatch is combined withfrom about 1 percent to about 10 percent by weight of a styrenic blockcopolymer mixed with from about 0.1 percent to about 30 percent byweight of a white mineral oil; from about 1 percent to about 50 percentby weight of a high density ethylene copolymer; and from about 1 percentto about 70 percent by weight of a hexene copolymer.
 9. A compositioncomprising a masterbatch formed from at least one fly ash having aplurality of ash particles, a coupling agent, an acid scavenger, an antioxidant, and a maleic anhydride grafted high carrier resin having a meltflow index selected to encapsulate a plurality of ash particles; and abase resin having selected physical properties.
 10. The composition ofclaim 9 further including a blend of mineral oil mixed with SEPTON®4033flakes, said blend being mixed into one of the masterbatch and thetarget resin.
 11. The composition of claim 9 wherein said masterbatchfurther includes an impact modifier, a low melt resin, and a fractionalmelt resin blended with one of and with both of the base resin and themasterbatch.
 12. The composition of claim 9 further including a resinhaving a low melt flow index combined with one of and with both of saidbase or target resin and with the masterbatch.
 13. A compositioncomprising: from about 1 percent by weight to about 70 percent by weightof a composition formed from about 30 percent to about 85 percent byweight of a blend of at least one fly ash, about 0.1 percent to about1.0 percent by weight of an acid scavenger; about 0.2 percent to about4.5 percent by weight of an antioxidant, about 5 to about 15 percent byweight of a coupling agent, about 14 percent to about 69 percent byweight of a maleic anhydride modified high density polyethylene; fromabout 1 percent to about 10 percent by weight of a copolymer mixed withfrom about 0.1 percent to about 1.0 percent by weight of a white mineraloil; from about 10 percent to about 50 percent by weight of a highdensity ethylene copolymer; and from about 30 percent to about 70percent by weight of a hexene copolymer.
 14. A thermoplastic compound,comprising: (a) from 20 to 70 weight percent of a polyolefin resin; (b)a fractional melt resin; (c) from 50 to 80 weight percent of fly ash;(d) maleated polyolefin.
 15. A method of forming a product, said methodcomprising: providing a fly ash filler; providing an acid scavenger;providing an antioxidant; providing a coupling agent; providing animpact modifier; providing a melt carrier resin; combining said fly ashfiller, said coupling agent, said impact modifier said acid scavenger,said antioxidant and said melt carrier resin in selected quantities toform a masterbatch providing a base resin in a form for mixing; andmelting and mixing said base resin and said masterbatch to form acomposition; processing said composition into a desired physical formhaving selected impact properties.
 16. A method of forming acomposition, said method comprising: providing one or more first fly ashmaterials; mechanically processing said one or more first fly ashmaterials to form a fly ash filler; providing an acid scavenger;providing an antioxidant; providing a coupling agent; providing animpact modifier; providing a melt carrier resin; combining said fly ashfiller, said coupling agent, said impact modifier said acid scavenger,said antioxidant and said melt carrier resin in selected quantities toform a composition: providing a base resin in a form for mixing;providing an oil and copolymer mixed together in a form for mixing;melting said base resin; mixing said base resin, and said oil andcopolymer in selected quantities to form a composition in liquid form;processing said composition into a desired physical form having selectedimpact properties
 17. A composition comprising a masterbatch formed froma coupling agent, and or a maleic anhydride grafted high carrier resinhaving a melt flow index selected to enhance the target resin; and abase resin having selected physical properties.
 18. The composition ofclaim 17 further including a blend of mineral oil mixed with SEPTON®4033flakes, said blend being mixed into one of the masterbatch and thetarget resin.
 19. The composition of claim 18 further including afractional melt resin blended with one of and with both of the baseresin and the masterbatch.
 20. The composition of claim 18 furtherincluding a resin having a low melt flow index combined with one of andwith both of said base or target resin and with the masterbatch.